Alkyl-substituted hydroxyaromatic compounds useful as a multifunctional viscosity index improver

ABSTRACT

An oil-soluble alkyl substituted hydroxyaromatic compound, wherein the alkyl-moiety of the aromatic compounds is derived from at least one ethylene alpha-olefin copolymer of greater or above 25,000 to about 5000,000 number average molecular weight, said copolymer containing from 30 to 80 weight percent ethylene and wherein at least about 30% of the polymer&#39;s chains contain terminal ethenylidene unsaturation. The Mannich Base condensates of this invention are useful as multifunctional viscosity index improvers for oleaginous compositions, particularly lubricating oil compositions.

This is a continuation of application Ser. No. 473,582, filed Feb. 1,1990, and now abandoned.

FIELD OF THE INVENTION

This invention relates to improved oil soluble compositions useful asadditives, particularly multifunctional viscosity index improveradditives, for oleaginous compositions, including fuel and lubricatingoil compositions, and to concentrates containing said additives.

BACKGROUND OF THE INVENTION

U.S. Pat. No. 3,442,808 relates to lubricating oil additives prepared byreacting alkenyl succinic anhydride with the Mannich condensationproduct prepared by condensing alkyl substituted phenol, formaldehydeand polyalkylene polyamine.

U.S. Pat. No. 3,458,495 relates to oxidation inhibitors anddispersant-detergent oil additives comprising the reaction product ofone equivalent of a phosphosulfurized hydrocarbon and about 0.5 to 4equivalents of an alkylene amino phenol. The phosphosulfurizedhydrocarbons are prepared by reacting a terpene, a petroleum fraction ora 500 to 200,000 molecular weight C₂ to C₆ olefin polymer (includingpolymers of ethylene, propylene, butylene, isobutylene or isoamylene)and from 5 to 40 wt % of a sulfide of phosphorous. The alkylene aminophenol is prepared by a Mannich Base condensation of aldehyde, alkylenepolyamine and alkyl phenol.

U.S. Pat. No. 4,354,950 disloses a method of preparing Mannich basederivatives of hydroxyaryl succinimides of the formula: ##STR1## whereinR is hydrocarbyl of 25 to 200 carbon atoms, R' is H, alkyl or halogen,"n" is 2 or 3, "m" has a value of 1 to 5, Y is H or a methylenehydroxyaryl succinimide radical, "x" has a value of 1 to 2 when Y is Hand a value of 1 when Y is a methylene hydroxyaryl succinimide radical.The above succinimides are formed in a stepwise reaction, e.g., byreacting a polyalkenyl succinic anhydride with an aminophenol, toproduce an intermediate N-(hydroxyaryl) hydrocarbyl succinimide, whichis then reacted with an alkylene diamine and an aldehyde (e.g.,formaldehyde) in a Mannich base reaction to produce the describedsuccinimides. The described succinimides may be added to a base oil oflubricating viscosity to form lubricant concentrates and lubricating oilformulations.

U.S. Pat. No. 4,668,834 to Uniroyal Chemical discloses preparation andcomposition of ethylene-alpha olefin copolymers and terpolymers, whichare disclosed to be useful as intermediates in epoxy-graftedencapsulation compositions.

Japanese Published Patent Application 87-129,303A of MitsuiPetrochemical relates to narrow molecular weight distribution (M_(w)/M_(n) <2.5) ethylene alpha-olefin copolymers containing 85-99 mol %ethylene, which are disclosed to be used for dispersing agents,modifiers or materials to produce toners. The copolymers (havingcrystallinity of from 5-85%) are prepared in the presence of a catalystsystem comprising Zr compounds having at least one cycloalkadienyl groupand alumoxane.

European Patent 128,046 discloses (co)polyolefin reactor blends ofpolyethylene and ethylene higher alpha-olefin copolymers prepared byemploying described dual-metallocene/alumoxane catalyst systems.

European Patent Publication 129,368 discloses metallocene/alumoxanecatalysts useful for the preparation of ethylene homopolymer andethylene higher alpha-olefin copolymers.

European Patent Application Publication 257,696 Al relates to a processfor dimerizing alpha-olefins using a catalyst comprising certainmetallocene/alumoxane systems.

PCT Published Patent Application WO 88/01626 relates to transition metalcompound/alumoxane catalysts for polymerizing alpha-olefins.

SUMMARY OF THE INVENTION

In accordance with one aspect of the present invention, there areprovided novel alkylated hydroxy aromatic compounds wherein thealkyl-moiety of the alkyl phenol is derived from at least one terminallyunsaturated ethylene alpha-olefin polymer of from greater than 20,000 toabout 500,000 number average molecular weight, wherein the terminalunsaturation comprises ethenylidene unsaturation.

In accordance with other aspects of the present invention, anoil-soluble lubricating oil additive is provided which comprises aMannich Base condensate of an alkyl substituted hydroxy aromaticcompound with formaldehyde and an amine, wherein the alkyl-moiety of thearomatic compounds is derived from at least one terminally unsaturatedethylene alpha-olefin copolymer of from greater than 20,000 to about500,000 number average molecular weight, wherein the terminalunsaturation comprises ethenylidene unsaturation.

The process of this invention permits the preparation of noveloil-soluble Mannich Base condensate lubricating oil additives which aresimultaneously characterized by a low concentration of unreacted polymer(usually less than about 40 wt %, e.g., from 5 to 35 wt %) and byadvantageous viscosity properties to permit the additives to be readilyhandled. The present invention can produce such substituted polymers ina highly concentrated form as substantially halogen free materials,thereby reducing the corrositivity processing difficulties andenvironmental concerns which are associated with halogen-containinglubricating oil additives.

The materials of the invention are different from the prior art MannichBase materials because of their effectiveness and their ability toprovide enhanced lubricating oil dispersancy.

DETAILED DESCRIPTION OF THE INVENTION PREPARATION OF ETHYLENEALPHA-OLEFIN COPOLYMER

The polymers employed in this invention are the formula H₂ C═CHR¹wherein R¹ is straight chain or branched chain alkyl radical comprising1 to 18 carbon atoms and wherein the polymer contains a high degree ofterminal ethenylidene unsaturation. Preferably R¹ in the above formulais alkyl of from 1 to 8 carbon atoms, and more preferably is alkyl offrom 1 to 2 carbon atoms. Therefore, useful comonomers with ethylene inthis invention include propylene, 1-butene, hexene-1, octene-1,4-methylpentene-1, decene-1, dodecene-1, tridecene-1, tetradecene-1,pentadecene-1, hexadecene-1, heptadecene-1, octadecene-1, nonadecene-1and mixtures thereof (e.g., mixtures of propylene and 1-butene, and thelike).

Exemplary of such polymers are ethylene-propylene copolymers,ethylene-butene-1 copolymers and the like. Preferred polymers arecopolymers of ethylene and propylene and ethylene and butene-1.

The molar ethylene content of the polymers employed in this invention ispreferably in the range of between about 20 and about 80 percent, andmore preferably between about 30 and about 70 percent. When propyleneand/or butene-1 are employed as comonomer(s) with ethylene, the ethylenecontent of such copolymers is most preferably between about 45 and about65 percent, although higher or lower ethylene contents may be present.

The polymers employed in this invention generally possess a numberaverage molecular weight of at least greater (above) than 20,000,preferably at least about 25,000, more preferably at least about 30,000,and most preferably at least about 30,000. Generally, the polymersshould not exceed a number average molecular weight of about 500,000,preferably about more preferably about 100,000, and most preferablyabout 50,000. The number average molecular weight for such polymers canbe determined by several known techniques. A convenient method for suchdetermination is by size exclusion chromatography (also known as gelpermeation chromatography (GPC)) which additionally provides molecularweight distribution information, see W. W. Yau, J. J. Kirkland and D. D.Bly, "Modern Size Exclusion Liquid Chromatography", John Wiley and Sons,New York, 1979.

The polymers employed in this invention preferably exhibit a degree ofcrystallinity such that, when functionalized, they are readily solublein mineral oils.

The polymers employed in this invention are further characterized inthat up to about 95% and more of the polymer chains possess terminalethenylidene-type unsaturation. Thus, one end of such polymers will beof the formula POLY-C(T¹)═CH₂ wherein T¹ is C₁ to C₁₈ alkyl, preferablyC₁ to C₈ alkyl, and more preferably C₁ to C₂ alkyl, (e.g., methyl orethyl) and wherein POLY represents the polymer chain. The chain lengthof the T¹ alkyl group will vary depending on the comonomer(s) selectedfor use in the polymerization. A minor amount of the polymer chains cancontain terminal ethenyl unsaturation, i.e. POLY-CH═CH₂, and a portionof the polymers can contain internal monounsaturation, e.g.POLY-CH═CH(T¹), wherein T¹ is as defined above.

The polymer employed in this invention comprises polymer chains, atleast about 30 percent of which possess terminal ethenylideneunsaturation. Preferably at least about 50 percent, more preferably atleast about 60 percent, and most preferably at least about 75 percent(e.g. 75-98%), of such polymer chains exhibit terminal ethenylideneunsaturation. The percentage of polymer chains exhibiting terminalethenylidene unsaturation may be determined by FTIR spectroscopicanalysis, titration, or C¹³ NMR.

The polymers employed in this invention may generally be preparedsubstantially in accordance with the procedures described in U.S. Pat.No. Nos. 4,752,597, and 4,871,705; in European Patent Publications128,046 and 129,368; in co-pending Ser. No. 728,111, now abandoned filedApr. 29, 1985; and copending Ser. No. 93,460 corresponding to U.S. Pat.No. 5,084,530, filed Sep. 10, 1987, the disclosures of all of which arehereby incorporated by reference in their entirety.

The polymers for use in the present invention can be prepared bypolymerizing monomer mixtures comprising ethylene in combination withother monomers such as alpha-olefins having from 3 to 20 carbon atoms(and preferably from 3-4 carbon atoms, i.e., propylene, butene-1, andmixtures thereof) in the presence of a catalyst system comprising atleast one metallocene (e.g., a cyclopentadienyl-transition metalcompound) and an alumoxane compound. The comonomer content can becontrolled through the selection of the metallocene catalyst componentand by controlling the partial pressure of the various monomers.

The catalysts employed in the production of the reactant polymers areorganometallic coordination compounds which are cyclopentadienylderivatives of a Group 4b metal of the Periodic Table of the Elements(56th Edition of Handbook of Chemistry and Physics, CRC Press [1975])and include mono, di and tricyclopentadienyls and their derivatives ofthe transition metals. Particularly desirable are the metallocene of aGroup 4b metal such as titanium, zirconium, and hafnium. The alumoxanesemployed in forming the reaction product with the metallocenes arethemselves the reaction products of an aluminum trialkyl with water.

In general, at least one metallocene compound is employed in theformation of the catalyst. As indicated, supra, metallocene is a metalderivative of a cyclopentadiene. The metallocenes usefully employed inaccordance with this invention contain at least one cyclopentadienering. The metal is selected from the Group 4b preferably titanium,zirconium, and hafnium, and most preferably hafnium and zirconium. Thecyclopentadienyl ring can be unsubstituted or contain one or moresubstituents (e.g., from 1 to 5 substituents) such as, for example, ahydrocarbyl substituent (e.g., up to 5 C₁ to C₅ hydrocarbylsubstituents) or other substituents, e.g. such as, for example, atrialkyl silyl substituent. The metallocene can contain one, two, orthree cyclopentadienyl rings; however, two rings are preferred.

Useful metallocenes can be represented by the general formulas:

    (Cp).sub.m MR.sub.n X.sub.q                                I.

wherein Cp is a cyclopentadienyl ring, M is a Group 4b transition metal,R is a hydrocarbyl group or hydrocarboxy group having from 1 to 20carbon atoms, X is a halogen, and m is a whole number from 1 to 3, n isa whole number from 0 to 3, and q is a whole number from 0 to 3.

    (C.sub.5 R'.sub.k).sub.g R".sub.s (C.sub.5 R'.sub.k)MQ.sub.3-gII.and

    R".sub.s (C.sub.5 R'.sub.k).sub.2 MQ'                      III.

wherein (C₅ R'_(k)) is a cyclopentadienyl or substitutedcyclopentadienyl, each R' is the same or different and is hydrogen or ahydrocarbyl radical such as alkyl, alkenyl, aryl, alkylaryl, orarylalkyl radical containing from 1 to 20 carbon atoms, a siliconcontaining hydrocarbyl radical, or hydrocarbyl radicals wherein twocarbon atoms are joined together to form a C₄ -C₆ ring, R" is a C₁ -C₄alkylene radical, a dialkyl germanium or silicon, or a alkyl phosphineor amine radical bridging two (C₅ R'_(k)) rings, Q is a hydrocarbylradical such as aryl, alkyl, alkenyl, alkylaryl, or aryl alkyl radicalhaving from 1-20 carbon atoms, hydrocarboxy radical having from 1-20carbon atoms or halogen and can be the same or different from eachother, Q, is an alkylidene radical having from 1 to about 20 carbonatoms, s is 0 or 1, g is 0, 1 or 2, s is 0 when g is 0, k is 4 when s is1, and k is 5 when s is 0, and M is as defined above. Exemplaryhydrocarbyl radicals are methyl, ethyl, propyl, butyl, amyl, isoamyl,hexyl, isobutyl, heptyl, octyl, nonyl, decyl, cetyl, 2-ethylhexyl,phenyl and the like. Exemplary silicon containing hydrocarbyl radicalsare trimethylsilyl, triethylsilyl and triphenylsilyl. Exemplary halogenatoms include chlorine, bromine, fluorine and iodine and of thesehalogen atoms, chlorine is preferred. Exemplary hydrocarboxy radicalsare methoxy ethoxy, butoxy, amyloxy and the like. Exemplary of thealkylidene radicals is methylidene, ethylidene and propylidene.

Illustrative, but non-limiting examples of the metallocenes representedby Formula I are dialkyl metallocenes such asbis(cyclopentadienyl)titanium dimethyl, bis(cyclopentadienyl)titaniumdiphenyl, bis(cyclopentadienyl)zirconium dimethyl,bis(cyclopentadienyl)zirconium diphenyl, bis(cyclopentadienyl)hafniumdimethyl and diphenyl, bis(cyclopentadienyl)titanium di-neopentyl,bis(cyclopentadienyl)zirconium di-neopentyl,bis(cyclopentadienyl)titanium dibenzyl, bis(cyclopentadienyl)zirconiumdibenzyl, bis(cyclopentadienyl)vanadium dimethyl; the mono alkylmetallocenes such as bis(cyclopentadienyl)titanium methyl chloride,bis(cyclopentadienyl) titanium ethyl chloridebis(cyclopentadienyl)titanium phenyl chloride,bis(cyclopentadienyl)zirconium hydrochloride,bis(cyclo-pentadienyl)zirconium methyl chloride,bis(cyclopentadienyl)zirconium ethyl chloride,bis(cyclopentadienyl)zirconium phenyl chloride,bis(cyclopentadienyl)titanium methyl bromide,bis(cyclopentadienyl)titanium methyl iodide,bis(cyclopentadienyl)titanium ethyl bromide, bis(cyclopentadienyl)titanium ethyl iodide, bis(cyclopentadienyl)titanium phenyl bromide,bis(cyclopentadienyl)titanium phenyl iodide,bis(cyclopentadienyl)zirconium methyl bromide,bis(cyclopentadienyl)zirconium methyl iodide,bis(cyclopentadienyl)zirconium ethyl bromide.bis(cyclopentadienyl)zirconium ethyl iodide,bis(cyclopentadienyl)zirconium phenyl bromide,bis(cyclopentadienyl)zirconium phenyl iodide; the trialkyl metallocenessuch as cyclopentadienyltitanium trimethyl, cyclopentadienyl zirconiumtriphenyl, and cyclopentadienyl zirconium trineopentyl,cyclopentadienylzirconium trimethyl, cyclopentadienylhafnium triphenyl,cyclopentadienylhafnium trineopentyl, and cyclopentadienylhafniumtrimethyl.

Illustrative, but non-limiting examples of II and III metallocenes whichcan be usefully employed are monocyclopentadienyls titanocenes such as,pentamethylcyclopentadienyl titanium trichloride,pentaethylcyclopentadienyl titanium trichloride,bis(pentamethylcyclopentadienyl) titanium diphenyl, the carbenerepresented by the formula bis(cyclopentadienyl)titanium═CH₂ andderivatives of this reagent such as bis(cyclopentadienyl)Ti═CH₂.Al(CH₃)₃, (Cp₂ TiCH₂)₂, Cp₂ TiCH₂ CH(CH₃)CH₂, Cp₂ Ti--CH₂ CH₂ CH₂ ;substituted bis(Cp)Ti(IV) compounds such as bis(indenyl) titaniumdiphenyl or dichloride, bis(methylcyclopentadienyl)titanium diphenyl ordihalides; dialkyl, trialkyl, tetra-alkyl and penta-alkylcyclopentadienyl titanium compounds such asbis(1,2-dimethylcyclopentadienyl)titanium diphenyl or dichloride,bis(1,2-diethylcyclopentadienyl)titanium diphenyl or dichloride andother dihalide complexes; silicon, phosphine, amine or carbon bridgedcyclopentadiene complexes, such as dimethylsilyldicyclopentadienyltitanium diphenyl or dichloride, methyl phosphine dicyclopentadienyltitanium diphenyl or dichloride, methylenedicyclopentadienyl titaniumdiphenyl or dichloride and other complexes described by formulae II andIII.

Illustrative but non-limiting examples of the zirconocenes of Formula IIand III which can be usefully employed are, pentamethylcyclopentadienylzirconium trichloride, pentaethylcyclopentadienyl zirconium trichloride,the alkyl substituted cyclopentadienes, such asbis(ethylcyclopentadienyl)zirconium dimethyl,bis(betaphenylpropylcyclopentadienyl) zirconium dimethyl,bis(methylcyclopentadienyl)zirconium dimethyl,bis(n-butylcyclopentadienyl)zirconium dimethylbis(cyclohexylmethylcyclopentadienyl)zirconium dimethylbis(n-octylcyclopentadienyl)zirconium dimethyl, and haloalkyl anddihydride, and dihalide complexes of the above; dialkyl, trialkyl,tetra-alkyl, and penta-alkyl cyclopentadienes, such asbis(pentamethylcyclopentadienyl)zirconium diphenyl,bis(pentamethylcyclopentadienyl)zirconium dimethyl,bis(1,2-dimethylcyclopentadienyl)zirconium dimethyl and mono anddihalide and hydride complexes of the above; silicon, phosphorus, andcarbon bridged cyclopentadiene complexes such asdimethylsilyldicyclopentadienyl zirconium dimethyl, methyl halide ordihalide, and methylene dicyclopentadienyl zirconium dimethyl, methylhalide, or dihalide. Mono, di and tri-silyl substituted cyclopentadienylcompounds such as bis(trimethylsilylcyclopentadienyl)zirconiumdichloride and dimethylbis(1,3-di-trimethylsilylcyclopentadienyl)zirconium dichloride anddimethyl and bis(1,2,4-tri-trimethylsilylcyclopentadienyl)zirconiumdichloride and dimethyl. Carbenes represented by the formulae Cp₂ Zr═CH₂P(C₆ H₅)₂ CH₃, and derivatives of these compounds such as Cp₂ ZrCH₂CH(CH₃)CH₂..

Mixed cyclopentadienyl metallocene compounds such as cyclopentadienyl(pentamethyl cyclopentadienyl)zirconium dichloride,(1,3-di-trimethylsilylcyclopentadienyl) (pentamethylcyclopentadienyl)zirconium dichloride, and cyclopentadienyl(indenyl) zirconium dichloridecan be employed.

Most preferably, the polymers used in this invention are substantiallyfree of ethylene homopolymer.

Bis(cyclopentadienyl)hafnium dichloride, bis(cyclopentadienyl)hafnium;dimethyl, bis(cyclopentadienyl)vanadium dichloride and the like areillustrative of other metallocenes.

Some preferred metallocenes are bis(cyclopentadienyl)zirconium;dimethyl, bis(cyclopentadienyl)zirconium dichloride;bis(cyclopentadienyl)titanium dichloride; bis(methylcyclopentadienyl)zirconium dichloride; bis(methylcyclopentadienyl)titanium dichloride;bis(n-butylcyclopentadienyl)zirconium dichloride;dimethylsilyldicyclopentadienyl zirconium dichloride;bis(trimethylsilycyclopentadienyl)zirconium dichloride; anddimethylsilyldicyclopentadienyl titanium dichloride;bis(indenyl)zirconium dichloride;bis(4,5,6,7-tetrahydroindenyl)zirconium dichloride; the racemic and/ormeso isomer of 1,2-ethylene-bridgedbis(4,5,6,7-tetrahydroindenyl)zirconium dichloride; the racemic and/ormeso isomer of 1,1-dimethylsilyl-bridgedbis(4,5,6,7-tetrahydroindenyl)zirconium dichloride; and the racemicand/or meso isomer of 1,1-dimethylsilyl-bridgedbis(methylcyclopentadienyl)zirconium dichloride.

The alumoxane compounds useful in the polymerization process may becyclic or linear. Cyclic alumoxanes may be represented by the generalformula (R--Al--O)_(n) while linear alumoxanes may be represented by thegeneral formula R(R--Al--O)_(n) 'AlR₂. In the general formula R is a C₁-C₅ alkyl group such as, for example, methyl, ethyl, propyl, butyl andpentyl, n is an integer of from 3 to 20, and n' is an integer from 1 toabout 20. Preferably, R is methyl and n and n' are 4-18. Generally, inthe preparation of alumoxanes from, for example, aluminum trimethyl andwater, a mixture of the linear and cyclic compounds is obtained.

The alumoxane can be prepared in various ways. Preferably, they areprepared by contacting water with a solution of aluminum trialkyl, suchas, for examples, aluminum trimethyl, in a suitable organic solvent suchas toluene or an aliphatic hydrocarbon. For example, the aluminum alkylis treated with water in the form of a moist solvent. In an alternativemethod, the aluminum alkyl such as aluminum trimethyl can be desirablycontacted with a hydrated salt such as hydrated copper sulfate orferrous sulfate. Preferably, the alumoxane is prepared in the presenceof a hydrated ferrous sulfate. The method comprises treating a dilutesolution of aluminum trimethyl in, for example, toluene, with ferroussulfate represented by the general formula FeSO₄.7H₂ O. The ratio offerrous sulfate to aluminum trimethyl is desirably about 1 mole offerrous sulfate for 6 to 7 moles of aluminum trimethyl. The reaction isevidenced by the evolution of methane.

The mole ratio of aluminum in the alumoxane to total metal in themetallocenes which can be usefully employed can be in the range of about0.5:1 to about 1000:1, and desirably about 1:1 to about 100:1.Preferably, the mole ratio will be in the range of 50:1 to about 5:1 andmost preferably 20:1 to 5:1.

The solvents used in the preparation of the catalyst system are inerthydrocarbons, in particular a hydrocarbon that is inert with respect tothe catalyst system. Such solvents are well known and include, forexample, isobutane, butane, pentane, hexane, heptane, octane,cyclohexane, methylcyclohexane, toluene, xylene and the like.

Polymerization is generally conducted at temperatures ranging betweenabout 20° and about 300° C., preferably between about 30° and about 200°C. Reaction time is not critical and may vary from several hours or moreto several minutes or less, depending upon factors such as reactiontemperature, the monomers to be copolymerized, and the like. One ofordinary skill in the art may readily obtain the optimum reaction timefor a given set of reaction parameters by routine experimentation.

The catalyst systems described herein are suitable for thepolymerization of olefins in solution over a wide range of pressures.Preferably, the polymerization will be completed at a pressure of fromabout 10 to about 3,000 bar, and generally at a pressure within therange from about 40 bar to about 2,000 bar, and most preferably, thepolymerization will be completed at a pressure within the range fromabout 50 bar to about 1,500 bar.

After polymerization and, optionally, deactivation of the catalyst(e.g., by conventional techniques such as contacting the polymerizationreaction medium with water or an alcohol, such as methanol, propanol,isopropanol, etc., or cooling or flashing the medium to terminate thepolymerization reaction), the product polymer can be recovered byprocesses well known in the art. Any excess reactants may be flashed offfrom the polymer.

The polymerization may be conducted employing liquid monomer, such asliquid propylene, or mixtures of liquid monomers (such as mixtures ofliquid propylene and 1-butene), as the reaction medium. Alternatively,polymerization may be accomplished in the presence of a hydrocarboninert to the polymerization such as butane, pentane, isopentane, hexane,isooctane, decane, toluene, xylene, and the like.

In those situations wherein the molecular weight of the polymer productthat would be produced at a given set of operating conditions is higherthan desired, any of the techniques known in the prior art for controlof molecular weight, such as the use of hydrogen and/or polymerizationtemperature control, may be used in the process of this invention. If sodesired, the polymerization may be carried out in the presence ofhydrogen to lower the polymer molecular weight. Care should be taken toassure that terminal ethenylidene unsaturation is not reduced to lessthan about 30 percent of the polymer chains.

However, the polymers are preferably formed in the substantial absenceof added H₂ gas, that is, the absence of H₂ gas added in amountseffective to substantially reduce the polymer molecular weight. Morepreferably, the polymerizations will be conducted employing less than 5wppm, and more preferably less than 1 wppm, of added H2 gas, based onthe moles of the ethylene monomer charged to the polymerization zone.

When carrying out the polymerization in a batch-type fashion, thereaction diluent (if any), ethylene and alpha-olefin comonomer(s) arecharged at appropriate ratios to a suitable reactor. Care must be takenthat all ingredients are dry, with the reactants typically being passedthrough molecular sieves or other drying means prior to theirintroduction into the reactor. Subsequently, either the catalyst andthen the cocatalyst, or first the cocatalyst and then the catalyst areintroduced while agitating the reaction mixture, thereby causingpolymerization to commence. Alternatively, the catalyst and cocatalystmay be premixed in a solvent and then charged to the reactor. As polymeris being formed, additional monomers may be added to the reactor. Uponcompletion of the reaction, unreacted monomer and solvent are eitherflashed or distilled off, if necessary by vacuum, and the low molecularweight copolymer withdrawn from the reactor.

The polymerization may be conducted in a continuous manner bysimultaneously feeding the reaction diluent (if employed), monomers,catalyst and cocatalyst to a reactor and withdrawing solvent, unreactedmonomer and polymer from the reactor so as to allow a residence time ofingredients long enough for forming polymer of the desired molecularweight and separating the polymer from the reaction mixture.

HYDROXYAROMATIC COMPOUNDS

The hydroxy aromatic compounds useful in the preparation of thealkylated materials of this invention include those compounds having theFormula (IIIa):

H--Ar--(OH)_(c)

wherein Ar represents ##STR2## wherein a is 1 or 2, R" is independentlya halogen radical such as the bromide or chloride radical, or ahydrocarbyl radical containing from 1 to about 10 carbon atoms,preferably an alkyl radical containing from 1 to about 10 carbon atoms,b is independently an integer from 0 to 2, and c is an integer from 1 to2.

Illustrative of such Ar groups are phenylene, biphenylene, naphthyleneand the like.

PREPARATION OF THE ALKYLATED HYDROXYAROMATIC COMPOUNDS

The selected ethylene alpha-olefin polymer and hydroxy aromatic compoundare contacted in the presence of a catalytically effective amount of atleast one acidic alkylation catalyst under conditions effective toalkylate the aromatic group of the hydroxy aromatic compound. Thealkylation catalyst is conventional and can comprise inorganic acidssuch as H₃ PO₄, H₂ SO₄, HF, BF₃, HF--BF₃ and the like. The acid catalystcan also comprise an acidic ion exchange resin having acidic groupsadsorbed or absorbed thereon, such as Amberlyst 15 resin (Rohm & HaasCo.), and the like. Also useful as catalysts are preformed complexes (orcomplexes formed in situ) of the foregoing with C₂ to C₁₀ ethers, C₁ toC₁₀ alcohols, C₂ to C₁₀ ketones, phenols and the like, such as BF₃complexed with dimethyl ether, diethyl ether, phenol, and the like.

The hydroxy aromatic compound and polymer will be generally contacted ina ratio of from about 0.1 to 10, preferably from about 1 to 7, morepreferably from about 2 to 5, moles of the aromatic compound per mole ofthe polymer. The selected acid catalyst can be employed in widelyvarying concentrations. Generally, when the acid catalyst comprises aninorganic catalyst, the acid catalyst will be charged to provide atleast about 0.001, preferably from about 0.01 to 0.5, more preferablyfrom about 0.1 to 0.3, moles of catalyst per mole of hydroxy aromaticcompound charged to the alkylation reaction zone. Use of greater than 1mole of the inorganic catalyst per mole of hydroxy aromatic compound isnot generally required. When the acid catalyst comprises a supportedcatalyst, such as an acidic ion exchange resin, the reactants can becontacted with the ion exchange resin employing any conventionalsolid-liquid contacting techniques, such as by passing the reactantsthrough the resin (e.g., in a catalyst bed or through a membraneimpregnated or otherwise containing the resin catalyst) and the upperlimit on the moles of catalyst employed per mole of hydroxy aromaticcompound is not critical.

The temperature for alkylation can also vary widely, and will usuallyrange from about 20° to 250° C., preferably from about 30° to 150° C.,more preferably from about 50° to 80° C.

The alkylation reaction time can vary and will generally be from about 1to 5 hours, although longer or shorter times can also be employed. Thealkylation process can be practiced in a batchwise, continuous orsemicontinuous manner. Preferably, the acid catalyst is neutralizedand/or removed prior to contacting the alkylation product mixture withthe nucleophilic reagent (e.g., polyamine) and aldehyde reactant. Theneutralization can be accomplished by contacting the crude alkylationproduct with gaseous ammonia or other basically reacting compound (e.g.,aqueous NaOH, KOH, and the like), followed by filtration to remove anyprecipitated neutralized catalyst solids.

Alkylation processes of the above types are known and are described, forexample, in U.S. Pat. Nos. 3,539,633 and 3,649,229, the disclosures ofwhich are hereby incorporated by reference.

It will be understood that the ethylene alpha-olefin polymers of thisinvention which are charged to the alkylation reaction zone can becharged alone or together with (e.g., in admixture with) otherpolyalkenes derived alkenes having from 1 to 20 carbon atoms (butene,pentene, octene, decene, dodecene, tetradodecene and the like) andhomopolymers of C₃ to C₁₀, e.g., C₂ to C₅, monoolefins, and copolymersof C₂ to C₁₀, e.g., C₂ to C₅, monoolefins, said additional polymerhaving a number average molecular weight of at least about 900, and amolecular weight distribution of less than about 4.0, preferably lessthan about 3.0 (e.g, from 1.2 to 2.8). Preferred such additional olefinpolymers comprise a major molar amount of C₂ to C₁₀, e.g. C₂ to C₅monoolefin. Such olefins include ethylene, propylene, butylene,isobutylene, pentene, octene-1, styrene, etc. Exemplary of theadditionally charged homopolymers is polypropylene, polyisobutylene, andpoly-n-butene the like as well as interpolymers of two or more of sucholefins such as copolymers of: ethylene and propylene (prepared byconventional methods other than as described above for the preferredethylene alpha-olefin copolymers employed in this invention, that is,ethylene-propylene copolymers which are substantially saturated, whereinless than about 10 wt. % of the polymer chains contain ethylenicunsaturation); butylene and isobutylene; propylene and isobutylene; etc.Other copolymers include those in which a minor molar amount of thecopolymer monomers, e.g., 1 to 10 mole %, is a C₄ to C₁₈ non-conjugateddiolefin, e.g., a copolymer of isobutylene and butadiene: or a copolymerof ethylene, propylene and 1,4-hexadiene; etc. The additional sucholefin polymers charged to the alkylation reaction will usually havenumber average molecular weights of at least about 900, more generallyat least about 1,500, more usually at least about 10,000. The uppernumber average molecular weight of such polymers should generally notexceed about 200,000, preferably about 100,000, and more preferablyabout 50,000. Particularly useful such additional olefin polymers havenumber average molecular weights within the range of about 1500 andabout 10,000 with approximately one double bond per chain. An especiallyuseful additional such polymer is polyisobutylene. Preferred aremixtures of such polyisobutylene with ethylene-propylene copolymerswherein at least 30 wt. % of the copolymer chains contain terminalethenylidene monounsaturation as described above.

The number average molecular weight for such polymers can be determinedby several known techniques. A convenient method for such determinationis by gel permeation chromatography (GPC) which additionally providesmolecular weight distribution information, see W. W. Yau, J. J. Kirklandand D. D. Bly, "Modern Size Exclusion Liquid Chromatography", John Wileyand Sons, New York, 1979.

THE ALDEHYDE MATERIAL

The aldehyde reactants will generally comprise formaldehyde orparaformaldehyde, although it will be understood that otheraldehyde-group containing compounds, such as C₂ to C₁₀ hydrocarbylaldehydes (e.g., butyraldehyde, acetaldehyde, propionaldehyde, and thelike) can also be employed. A preferred group of aldehyde materials arecompounds of the formula: R¹² CHO, wherein R¹² is H or aliphatichydrocarbon radical having from 1 to 4 carbon atoms.

AMINE COMPOUNDS

Amine compounds useful as nucleophilic reactants for reaction with theselected ethylene-alpha-olefin polymer and aldehyde materials includemono- and (preferably) polyamines, of about 2 to 60, preferably 2 to 40(e.g. 3 to 20), total carbon atoms and about 1 to 12, preferably 3 to12, and most preferably 3 to 9 nitrogen atoms in the molecule. Theseamines may be hydrocarbyl amines or may be hydrocarbyl amines includingother groups, e.g, hydroxy groups, alkoxy groups, amide groups,nitriles, imidazoline groups, and the like. Hydroxy amines with 1 to 6hydroxy groups, preferably 1 to 3 hydroxy groups are particularlyuseful. Preferred amines are aliphatic saturated amines, including thoseof the general formulas: ##STR3## wherein R, R', R" and R"' areindependently selected from the group consisting of hydrogen; C₁ to C₂₅straight or branched chain alkyl radicals; C₁ to C₁₂ alkoxy C₂ to C₆alkylene radicals; C₂ to C₁₂ hydroxy amino alkylene radicals; and C₁ toC₁₂ alkylamino C₂ to C₆ alkylene radicals; and wherein R"' canadditionally comprise a moiety of the formula: ##STR4## wherein R' is asdefined above, and wherein r and r' can be the same or a differentnumber of from 2 to 6, preferably 2 to 4; and t and t' can be the sameor different and are numbers of from 0 to 10, preferably 2 to 7, andmost preferably about 3 to 7, with the proviso that the sum of t and t'is not greater than 15. To assure a facile reaction, it is preferredthat R, R', R", R"', r, r', t and t' be selected in a manner sufficientto provide the compounds of Formulas IV and V with typically at leastone primary or secondary amine group, preferably at least two primary orsecondary amine groups. This can be achieved by selecting at least oneof said R, R', R" , or R"' groups to be hydrogen or by letting t inFormula V be at least one when R", is H or when the VI moiety possessesa secondary amino group. The most preferred amine of the above formulasare represented by Formula V and contain at least two primary aminegroups and at least one, and preferably at least three, secondary aminegroups.

Non-limiting examples of suitable amine compounds include:1,2-diaminoethane; 1,3-diaminopropane; 1,4-diaminobutane;1,6-diaminohexane; polyethylene amines such as diethylene triamine;triethylene tetramine; tetraethylene pentamine; polypropylene aminessuch as 1,2-propylene diamine; di-(1,2-propylene)triamine;di-(1,3-propylene) triamine; N,N-dimethyl-1,3-diaminopropane;N,N-di-(2-aminoethyl) ethylene diamine;N,N-di(2-hydroxyethyl)-1,3-propylene diamine; 3-dodecyloxypropylamine;N-dodecyl-1,3-propane diamine; tris hydroxymethylaminomethane (THAM);diisopropanol amine; diethanol amine; triethanol amine; mono-, di-, andtri-tallow amines; amino morpholines such asN-(3-aminopropyl)morpholine; and mixtures thereof.

Other useful amine compounds include: alicyclic diamines such as1,4-di(aminomethyl) cyclohexane, and heterocyclic nitrogen compoundssuch as imidazolines, and N-aminoalkyl piperazines of the generalFormula (VII): ##STR5## wherein p₁ and p₂ are the same or different andare each integers of from 1 to 4, and n₁, n₂ and n₃ are the same ordifferent and are each integers of from 1 to 3. Non-limiting examples ofsuch amines include 2-pentadecyl imidazoline; N-(2-aminoethyl)piperazine; etc.

Commercial mixtures of amine compounds may advantageously be used. Forexample, one process for preparing alkylene amines involves the reactionof an alkylene dihalide (such as ethylene dichloride or propylenedichloride) with ammonia, which results in a complex mixture of alkyleneamines wherein pairs of nitrogens are joined by alkylene groups, formingsuch compounds as diethylene triamine, triethylenetetramine,tetraethylene pentamine and isomeric piperazines. Low costpoly(ethyleneamines) compounds averaging about 5 to 7 nitrogen atoms permolecule are available commercially under trade names such as "PolyamineH", "Polyamine 400", "Dow Polyamine E-100", etc.

Useful amines also include polyoxyalkylene polyamines such as those ofthe Formula (VIII): ##STR6## where m has a value of about 3 to 70 andpreferably 10 to 35: and the Formula (IX): ##STR7## where n"' has avalue of about 1 to 40 with the provision that the sum of all the n"'values is from about 3 to about 70 and preferably from about 6 to about35, and R⁴ is a polyvalent saturated hydrocarbon radical of up to tencarbon atoms wherein the number of substituents on the R⁸ group isrepresented by the value of "a", which is a number of from 3 to 6. Thealkylene groups in either Formula (VII) or (IX) may be straight orbranched chains containing about 2 to 7, and preferably about 2 to 4carbon atoms.

The polyoxyalkylene polyamines of formulas (VII) or (IX) above,preferably polyoxyalkylene diamines and polyoxyalkylene triamines, mayhave average molecular weights ranging from about 200 to about 4000 andpreferably from about 400 to about 2000. The preferred polyoxyalkylenepolyoxyalkylene polyamines include the polyoxyethylene andpolyoxypropylene diamines and the polyoxypropylene triamines havingaverage molecular weights ranging from about 200 to 2000. Thepolyoxyalkylene polyamines are commercially available and may beobtained, for example, from the Jefferson Chemical Company, Inc. underthe trade name "Jeffamines D-230, D-400, D-1000, D-2000, T-403", etc.

A particularly useful class of amines are the polyamido and relatedamines disclosed in co-pending Ser. No. 126,405, filed Nov. 30, 1987,which comprise reaction products of a polyamine and an alpha, betaunsaturated compound of the formula: ##STR8## wherein X is sulfur oroxygen, Y is --OR⁸, --SR⁸, or --NR⁸ (R⁹), and R⁵, R⁶, R⁷, R⁸ and R⁹ arethe same or different and are hydrogen or substituted or unsubstitutedhydrocarbyl. Any polyamine, whether aliphatic, cycloaliphatic, aromatic,heterocyclic, etc., can be employed provided it is capable of addingacross the acrylic double bond and amidifying with for example thecarbonyl group (--C(O)--) of the acrylate-type compound of Formula X, orwith the thiocarbonyl group (--C(S)--) of the thioacrylate-type compoundof Formula X.

When R⁵, R⁶, R⁷, R⁸ or R⁹ in Formula X are hydrocarbyl, these groups cancomprise alkyl, cycloalkyl, aryl, alkaryl, aralkyl or heterocyclic,which can be substituted with groups which are substantially inert toany component of the reaction mixture under conditions selected forpreparation of the amido-amine. Such substituent groups include hydroxy,halide (e.g., Cl, Fl, I, Br), --SH and alkylthio. When one or more of R⁵through R⁹ are alkyl, such alkyl groups can be straight or branchedchain, and will generally contain from 1 to 20, more usually from 1 to10, and preferably from 1 to 4, carbon atoms. Illustrative of such alkylgroups are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl,nonyl, decyl, dodecyl, tridecyl, hexadecyl, octadecyl and the like. Whenone or more of R⁵ through R⁹ are aryl, the aryl group will generallycontain from 6 to 10 carbon atoms (e.g., phenyl, naphthyl).

When one or more of R⁵ through R⁹ are alkaryl, the alkaryl group willgenerally contain from about 7 to 20 carbon atoms, and preferably from 7to 12 carbon atoms. Illustrative of such alkaryl groups are tolyl,m-ethylphenyl, o-ethyltolyl, and m-hexyltolyl. When one or more of R⁵through R⁹ are aralkyl, the aryl component generally consists of phenylor (C₁ to C₆) alkyl-substituted phenol and the alkyl component generallycontains from 1 to 12 carbon atoms, and preferably from 1 to 6 carbonatoms. Examples of such aralkyl groups are benzyl, o-ethylbenzyl, and4-isobutylbenzyl. When one or more of R⁵ and R⁹ are cycloalkyl, thecycloalkyl group will generally contain from 3 to 12 carbon atoms, andpreferably from 3 to 6 carbon atoms. Illustrative of such cycloalkylgroups are cyclopropyl, cyclobutyl, cyclohexyl, cyclooctyl, andcyclododecyl. When one or more of R⁵ through R⁹ are heterocyclic, theheterocyclic group generally consists of a compound having at least onering of 6 to 12 members in which one or more ring carbon atoms isreplaced by oxygen or nitrogen. Examples of such heterocyclic groups arefuryl, pyranyl, pyridyl, piperidyl, dioxanyl, tetrahydrofuryl, pyrazinyland 1,4-oxazinyl.

The alpha, beta ethylenically unsaturated carboxylate compounds employedherein have the following formula: ##STR9## wherein R⁵, R⁶, R⁷, and R⁸are the same or different and are hydrogen or substituted orunsubstituted hydrocarbyl as defined above. Examples of such alpha,beta-ethylenically unsaturated carboxylate compounds of Formula XI areacrylic acid, methacrylic acid, the methyl, ethyl, isopropyl, n-butyl,and isobutyl esters of acrylic and methacrylic acids, 2-butenoic acid,2-hexenoic acid, 2-decenoic acid, 3-methyl-2-heptenoic acid,3-methyl-2-butenoic acid, 3-phenyl-2-propenoic acid,3-cyclohexyl-2-butenoic acid, 2-methyl-2-butenoic acid,2-propyl-2-propenoic acid, 2-isopropyl-2-hexenoic acid,2,3-dimethyl-2-butenoic acid, 3-cyclohexyl-2-methyl-2-pentenoic acid,2-propenoic acid, methyl 2-propenoate, methyl 2-methyl 2-propenoate,methyl 2-bentenoate, ethyl 2-hexenoate, isopropyl 2-decenoate, phenyl2-pentenoate, tertiary butyl 2-propenoate, octadecyl 2-propenoate,dodecyl 2-decenoate, cyclopropyl 2,3-dimethyl-2-butenoate, methyl3-phenyl-2-propenoate, and the like.

The alpha, beta ethylenically unsaturated carboxylate thioestercompounds employed herein have the following formula: ##STR10## whereinR⁵, R⁶, R⁷, and R⁸ are the same or different and are hydrogen orsubstituted or unsubstituted hydrocarbyl as defined above. Examples ofsuch alpha, beta-ethylenically unsaturated carboxylate thioesters ofFormula XII are methylmercapto 2-butenoate, ethylmercapto 2-hexenoate,isopropylmercapto 2-decenoate, phenylmercapto 2-pentenoate, tertiarybutylmercapto 2-propenoate, octadecylmercapto 2-propenoate,dodecylmercapto 2-decenoate, cyclopropylmercapto2,3-dimethyl-2-butenoate, methylmercapto 3-phenyl-2-propenoate,methylmercapto 2-propenoate, methylmercapto 2-methyl-2-propenoate, andthe like.

The alpha, beta ethylenically unsaturated carboxyamide compoundsemployed herein have the following formula: ##STR11## wherein R⁵, R⁶,R⁷, R⁸ and R⁹ are the same or different and are hydrogen or substitutedor unsubstituted hydrocarbyl as defined above. Examples of alpha,beta-ethylenically unsaturated carboxyamides of Formula XIII are2-butenamide, 2-hexenamide, 2-decenamide, 3-methyl-2-heptenamide,3-methyl-2-butenamide, 3-phenyl-2-propenamide,3-cyclohexyl-2-butenamide, 2-methyl-2-butenamide,2-propyl-2-propenamide, 2-isopropyl-2-hexenamide,2,3-dimethyl-2-butenamide, 3-cyclohexyl- 2-methyl-2-pentenamide,N-methyl 2-butenamide, N,N-diethyl 2-hexenamide, N-isopropyl2-decenamide, N-phenyl 2-pentenamide, N-tertiary butyl 2-propenamide,N-octadecyl 2-propenamide, N-N-didodecyl 2-decenamide, N-cyclopropyl2,3-dimethyl-2-butenamide, N-methyl 3-phenyl-2-propenamide,2-propenamide, 2-methyl-2-propenamide, 2-ethyl-2-propenamide and thelike.

The alpha, beta ethylenically unsaturated thiocarboxylate compoundsemployed herein have the following formula: ##STR12## wherein R⁵, R⁶,R⁷, R⁸ and R⁹ are the same or different and are hydrogen or substitutedor unsubstituted hydrocarbyl as defined above. Examples of alpha,beta-ethylenically unsaturated thiocarboxylate compounds of Formula XIVare 2-butenthioic acid, 2-hexenthioic acid, 2-decenthioic acid,3-methyl-2-heptenthioic acid, 3-methyl-2-butenthioic acid,3-phenyl-2-propenthioic acid, 3-cyclohexyl-2-butenthioic acid,2-methyl-2-butenthioic acid, 2-propyl-2-propenthioic acid,2-isopropyl-2-hexenthioic acid, 2,3-dimethyl-2-butenthioic acid,3-cyclohexyl-2-methyl-2-pententhioic acid, 2-propenthioic acid, methyl2-propenthioate, methyl 2-methyl 2-propenthioate, methyl 2-butenthioate,ethyl 2-hexenthioate, isopropyl 2-decenthioate, phenyl 2-pententhioate,tertiary butyl 2-propenthioate, octadecyl 2-propenthioate, dodecyl2-decenthioate, cyclopropyl 2,3-dimethyl-2-butenthioate, methyl3-phenyl-2-propenthioate, and the like.

The alpha, beta ethylenically unsaturated dithioic acid and acid estercompounds employed herein have the following formula: ##STR13## whereinR⁵, R⁶, R⁷, and R⁸ are the same or different and are hydrogen orsubstituted or unsubstituted hydrocarbyl as defined above. Examples ofalpha, beta-ethylenically unsaturated dithioic acids and acid esters ofFormula XV are 2-butendithioic acid, 2-hexendithioic acid,2-decendithioic acid, 3-methyl-2-heptendithioic acid,3-methyl-2-butendithioic acid, 3-phenyl-2-propendithioic acid,3-cyclohexyl-2-butendithioic acid, 2-methyl-2-butendithioic acid,2-propyl-2-propendithioic acid, 2-isopropyl-2-hexendithioic acid,2,3-dimethyl-2-butendithioic acid,3-cyclohexyl-2-methyl-2-pentendithioic acid, 2-propendithioic acid,methyl 2-propendithioate, methyl 2-methyl 2-propendithioate, methyl2-butendithioate, ethyl 2-hexendithioate, isopropyl 2-decendithioate,phenyl 2-pentendithioate, tertiary butyl 2-propendithioate, octadecyl2-propendithioate, dodecyl 2-decendithioate, cyclopropyl2,3-dimethyl-2-butendithioate, methyl 3-phenyl-2-propendithioate, andthe like.

The alpha, beta ethylenically unsaturated thiocarboxyamide compoundsemployed herein have the following formula: ##STR14## wherein R⁵, R⁶,R⁷, R⁸ and R⁹ are the same or different and are hydrogen or substitutedor unsubstituted hydrocarbyl as defined above. Examples of alpha,beta-ethylenically unsaturated thiocarboxyamides of Formula XVI are2-butenthioamide, 2-hexenthioamide, 2-decenthioamide,3-methyl-2-heptenthioamide, 3-methyl-2-butenthioamide,3-phenyl-2-propenthioamide, 3-cyclohexyl-2-butenthioamide,2-methyl-2-butenthioamide, 2-propyl-2-propenthioamide,2-isopropyl-2-hexenthioamide, 2,3-dimethyl-2-butenthioamide,3-cyclohexyl-2-methyl-2-pententhioamide, N-methyl 2-butenthioamide,N,N-diethyl 2-hexenthioamide, N-isopropyl 2-decenthioamide, N-phenyl2-pententhioamide, N-tertiary butyl 2-propenthioamide, N-octadecyl2-propenthioamide, N-N-didodecyl 2-decenthioamide, N-cyclopropyl2,3-dimethyl-2-butenthioamide, N-methyl 3-phenyl-2-propenthioamide,2-propenthioamide, 2-methyl-2-propenthioamide, 2-ethyl-2-propenthioamideand the like.

Preferred compounds for reaction with the polyamines in accordance withthis invention are lower alkyl esters of acrylic and (lower alkyl)substituted acrylic acid. Illustrative of such preferred compounds arecompounds of the formula: ##STR15## where R⁷ is hydrogen or a C₁ to C₄alkyl group, such as methyl, and R⁸ is hydrogen or a C₁ to C₄ alkylgroup, capable of being removed so as to form an amido group, forexample, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl,aryl, hexyl, etc. In the preferred embodiments these compounds areacrylic and methacrylic esters such as methyl or ethyl acrylate, methylor ethyl methacrylate. When the selected alpha, beta-unsaturatedcompound comprises a compound of Formula X wherein X' is oxygen, theresulting reaction product with the polyamine contains at least oneamido linkage (--C(O)N<) and such materials are herein termed"amido-amines." Similarly, when the selected alpha, beta unsaturatedcompound of Formula X comprises a compound wherein X' is sulfur, theresulting reaction product with the polyamine contains thioamide linkage(--C(S)N<) and these materials are herein termed "thioamido-amines." Forconvenience, the following discussion is directed to the preparation anduse of amido-amines, although it will be understood that such discussionis also applicable to the thioamido-amines.

The type of amido-amine formed varies with reaction conditions. Forexample, a more linear amido-amine is formed where substantiallyequimolar amounts of the unsaturated carboxylate and polyamine arereacted. The presence of excesses of the ethylenically unsaturatedreactant of Formula X tends to yield an amido-amine which is morecross-linked than that obtained where substantially equimolar amounts ofreactants are employed. Where for economic or other reasons across-linked amido-amine using excess amine is desired, generally amolar excess of the ethylenically unsaturated reactant of about at least10%, such as 10-300%, or greater, for example, 25-200%, is employed. Formore efficient cross-linking an excess of carboxylated material shouldpreferably be used since a cleaner reaction ensues. For example, a molarexcess of about 10-100% or greater such as 10-50%, but preferably anexcess of 30-50%, of the carboxylated material. Larger excess can beemployed if desired.

In summary, without considering other factors, equimolar amounts ofreactants tend to produce a more linear amido-amine whereas excess ofthe Formula XII reactant tends to yield a more cross-linked amido-amine.It should be noted that the higher the polyamine (i.e., in greater thenumber of amino groups on the molecule) the greater the statisticalprobability of cross-linking since, for example, atetraalkylenepentamine, such as tetraethylene pentamine ##STR16## hasmore labile hydrogens than ethylene diamine.

These amido-amine adducts so formed are characterized by both amido andamino groups, as represented, for example, by the following formula##STR17## wherein Z may be represented by units of the followingidealized Formula (XVIII): ##STR18## wherein the R¹⁰ s, which may be thesame or different, are hydrogen or a substituted group, such as ahydrocarbon group, for example, alkyl, alkenyl, alkynyl, aryl, etc., andA is a moiety of the polyamine which, for example, may be aryl,cycloalkyl, alkyl, etc., and n₄ is an integer such as 1-10 or greater.

The above simplified formula represents a linear amido-amine polymer.However, cross-linked polymers may also be formed by employing certainconditions since the polymer has labile hydrogens which can furtherreact with either the unsaturated moiety by adding across the doublebond or by amidifying with a carboxylate group.

Preferably, however, the amido-amines employed in this invention are notcross-linked to any substantial degree, and more preferably aresubstantially linear.

Preferably, the polyamine reactant contains at least one primary amine(and more preferably from 2 to 4 primary amines) group per molecule, andthe polyamine and the unsaturated reactant of Formula X are contacted inan amount of from about 1 to 10, more preferably from about 2 to 6, andmost preferably from about 3 to 5, equivalents of primary amine in thepolyamine reactant per mole of the unsaturated reactant of Formula X.

The reaction between the selected polyamine and acrylate-type compoundis carried out at any suitable temperature. Temperatures up to thedecomposition points of reactants and products can be employed. Inpractice, one generally carries out the reaction by heating thereactants below 100 C, such as 80°-90° C., for a suitable period oftime, such as a few hours. Where an acrylic-type ester is employed, theprogress of the reaction can be judged by the removal of the alcohol informing the amide. During the early part of the reaction, alcohol isremoved quite readily below 100° C. in the case of low boiling alcoholssuch as methanol or ethanol. As the reaction slows, the temperature israised to push the polymerization to completion and the temperature maybe raised to 150° C. toward the end of the reaction. Removal of alcoholis a convenient method of judging the progress and completion of thereaction which is generally continued until no more alcohol is evolved.Based on removal of alcohol, the yields are generally stoichiometric. Inmore difficult reactions, yield of at least 95% are generally obtained.

Similarly, it will be understood that the reaction of an ethylenicallyunsaturated carboxylate thioester of Formula XII liberates thecorresponding HSR⁸ compound (e.g., H₂ S when R⁸ is hydrogen) as aby-product, and the reaction of an ethylenically unsaturatedcarboxyamide of Formula XIII liberates the corresponding HNR⁸ (R⁹)compound (e.g., ammonia when R⁸ and R⁹ are each hydrogen) as by-product.

The reaction time to form an amido-amine material can vary widelydepending on a wide variety of factors. For example, there is arelationship between time and temperature. In general, lower temperaturedemands longer times. Usually, reaction times of from about 2 to 30hours, such as 5 to 25 hours, and preferably 3 to 10 hours will beemployed. Although one can employ a solvent, the reaction can be runwithout the use of any solvent. In fact, where a high degree ofcross-linking is desired, it is preferably to avoid the use of a solventand most particularly to avoid a polar solvent such as water. However,taking into consideration the effect of solvent on the reaction, wheredesired, any suitable solvent can be employed, whether organic orinorganic, polar or non-polar.

As an example of the amido-amine adducts, the reaction of tetraethylenepentamine (TEPA) with methyl methacrylate can be illustrated as follows:##STR19##

CONDENSATION REACTION

The Mannich Base condensate compositions of this invention are preparedby condensing at least one of the above described alkylatedhydroxyaromatic compounds with an amine in the presence of an aldehyde.The reactants are contacted for a time and under conditions sufficientto form the desired dispersant product.

The process employed in the condensation reaction can be any of thosedisclosed in U.S. Pat. Nos. 3,634,515; 3,649,229; 3,442,808; 3,798,165;3,798,247; and 3,539,633, the disclosures of which are herebyincorporated by reference in their entirety.

The amount of the reactants employed is not critical and can vary over awide range. It is, however, preferred to react the alkylated hydroxyaromatic compound, aldehyde reactant and amine compound in therespective molar ratios of about 1:1-4:0.1-10. An excess of aldehydereactant may be used. The reactions are exothermic, but it is desirableto heat the reaction to a temperature of above about 50° C., preferablyin the range of from about 50°-140° C. This additional heating drivesthe reaction to completion and removes water from the resultantcondensation reaction product.

The condensation reaction can be illustrated by the following reactionsemploying an alkylene polyamine and formaldehyde: ##STR20## wherein "z"is an integer of from 1 to 10, "a" is an integer of 1 or 2 and "EP" isan ethylene-propylene copolymer as described above, and ##STR21##wherein "z", and "EP" are as defined above.

A preferred group of Mannich Base multifunctional viscosity indeximprovers are those formed by condensing ethylene-propylenecopolymer-substituted phenol with formaldehyde and polyethylene amines,e.g., tetraethylene pentamine, pentaethylene hexamine, polyoxyethyleneand polyoxypropylene amines, e.g., polyoxypropylene diamine, andcombinations thereof. One particularly preferred multifunctionalviscosity index improver comprises a condensation of (A)ethylene-propylene copolymer-substituted phenol, (B) formaldehyde, (C) apolyoxyalkylene polyamine, e.g., polyoxypropylene diamine, and (D) apolyalkylene polyamine, e.g. polyethylene diamine and tetraethylenepentamine, using about 2 to about 8 moles each of (B) and about 1 toabout 4 moles of (C) or (D) per mole of (A).

The reaction product mixture comprising the desiredethylene-alpha-olefin substituted Mannich Base condensation productformed by the process of this invention will generally be present in thecondensation reaction product mixture in a concentration of at leastabout 60 wt % (e.g., from 65 to 95 wt %), more preferably at least about70 wt %, (e.g. from 75 to 90 wt %).

Another aspect of this invention involves the post treatment of thenitrogen containing multifunctional viscosity index improver materials.The process for post-treating said nitrogen containing multifunctionalviscosity index improver materials is analogous to the post-treatingprocesses used with respect to derivatives of conventional ethylenecopolymers of the prior art. Accordingly, the same reaction conditions,ratio of reactants and the like can be used.

The nitrogen-containing multifunctional viscosity index improvermaterials of the instant invention as described above are post-treatedby contacting said nitrogen-containing multifunctional viscosity indeximprover materials with one or more post-treating reagents selected fromthe group consisting of boron oxide, boron oxide hydrate, boron halides,boron acids, esters of boron acids, carbon disulfide, sulfur, sulfurchlorides, alkenyl cyanides, aldehydes, ketones, urea, thio-urea,guanidine, dicyanodiamide, hydrocarbyl phosphates, hydrocarbylphosphites, hydrocarbyl thiophosphates, hydrocarbyl thiophosphites,phosphorus sulfides, phosphorus oxides, phosphoric acid, hydrocarbylthiocyanates, hydrocarbyl isocyanates, hydrocarbyl isothiocyantes,epoxides, episulfides, formaldehyde or formaldehyde-producing compoundsplus phenols, and sulfur plus phenols, and C₁ to C₃₀ hydrocarbylsubstituted succinic acids and anhydrides (e.g., succinic anhydride,dodecyl succinic anhydride and the like), fumaric acid, itaconic acid,maleic acid, maleic anhydride, chloromaleic acid, chloromaleicanhydride, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid,and lower alkyl (e.g., C₁ to C₄ alkyl) acid esters of the foregoing,e.g., methyl maleate, ethyl fumarate, methyl fumarate, and the like.

For example, the nitrogen containing multifunctional viscosity indeximprovers can be treated with a boron compound selected from the classconsisting of boron oxide, boron halides, boron acids and esters ofboron acids in an amount to provide from about 0.1 atomic proportion ofboron for each mole of said nitrogen composition to about 20 atomicproportions of boron for each atomic proportion of nitrogen of saidnitrogen composition. Usefully the borated materials of the inventioncontain from about 0.05 to 2.0 wt. %, e.g. 0.05 to 0.7 wt. % boron basedon the total weight of said borated nitrogen-containing multifunctionalviscosity index improver compound. The boron, which appears to be in theproduct as dehydrated boric acid polymers (primarily (HBO₂)₃), isbelieved to attach to the multifunctional viscosity index improver asamine salts, e.g., the metaborate salt of said amine dispersants.

Treating is readily carried out by adding from about 0.05 to 4, e.g. 1to 3 wt. % (based on the weight of said nitrogen compound) of said boroncompound, preferably boric acid which is most usually added as a slurryto said nitrogen compound and heating with stirring at from about 135°C. to 190°, e.g. 140°-170° C., for from 1 to 5 hours followed bynitrogen stripping at said temperature ranges.

Since post-treating processes involving the use of these post-treatingreagents is known insofar as application to high molecular weightnitrogen-containing compounds of the prior art, further descriptions ofthese processes herein is unnecessary. In order to apply the prior artprocesses to the compositions of this invention, all that is necessaryis that reaction conditions, ratio of reactants, and the like asdescribed in the prior art, be applied to the novel compositions of thisinvention. The following U.S. patents are expressly incorporated hereinby reference for their disclosure of post-treating processes andpost-treating reagents applicable to the compositions of this invention:U.S. Pat. Nos. 3,087,936; 3,200,107; 3,254,025; 3,256,185; 3,278,550;3,281,428; 3,282,955; 3,284,410; 3,338,832, 3,344,069; 3,366,569;3,373,111; 3,367,943; 3,403,102; 3,428,561; 3,502,677; 3,513,093;3,533,945; 3,541,012; 3,639,242; 3,708,522; 3,859,318; 3,865,813;3,470,098; 3,369,021; 3,184,411; 3,185,645; 3,245,908; 3,245,909;3,245,910; 3,573,205; 3,692,681; 3,749,695; 3,865,740; 3,954,639;3,458,530; 3,390,086; 3,367,943; 3,185,704, 3,551,466; 3,415,750;3,312,619; 3,280,034; 3,718,663; 3,652,616; UK pat. No. 1,085,903; UKPat. No. 1,162,436; U.S. Pat. No. 3,558,743.

The nitrogen containing multifunctional viscosity index improvermaterials of this invention can also be treated with polymerizablelactones (such as epsilon-caprolactone) to form dispersant adductshaving the moiety --[C(O)(CH₂)_(z) O]_(m) H, wherein z is a number offrom 4 to 8 (e.g., 5 to 7) and m has an average value of from about 0 to100 (e.g., 0.2 to 20). The materials of this invention can bepost-treated with a C₅ to C₉ lactone, e.g., epsilon-caprolactone, byheating a mixture of the multifunctional viscosity index improvermaterial and lactone in a reaction vessel in the absence of a solvent ata temperature of about 50° C. to about 200° C., more preferably fromabout 75° C. to about 175° C., and most preferably from about 90° C. toabout 160° C., for a sufficient period of time to effect reaction.Optionally, a solvent for the lactone, multifunctional viscosity indeximprover material and/or the resulting adduct may be employed to controlviscosity and/or the reaction rates.

In one preferred embodiment, the C₅ to C₉ lactone, e.g.,epsilon-caprolactone, is reacted with a multifunctional viscosity indeximprover material in a 1:1 mole ratio of lactone to multifunctionalviscosity index improver material. In practice, the ratio of lactone tomultifunctional viscosity index improver material may vary considerablyas a means of controlling the length of the sequence of the lactoneunits in the adduct. For example, the mole ratio of the lactone to themultifunctional viscosity index improver material may vary from about10:1 to about 0.1:1, more preferably from about 5:1 to about 0.2:1, andmost preferably from about 2:1 to about 0.4:1. It is preferable tomaintain the average degree of polymerization of the lactone monomerbelow about 100, with a degree of polymerization on the order of fromabout 0.2 to about 50 being preferred, and from about 0.2 to about 20being more preferred.

Catalysts useful in the promotion of the lactone-multifunctionalviscosity index improver material reactions are selected from the groupconsisting of stannous octanoate, stannous hexanoate, tetrabutyltitanate, a variety of organic based acid catalysts and amine catalysts,as described on page 266, and forward, in a book chapter authored by R.D. Lundberg and E. F. Cox, entitled "Kinetics and Mechanisms ofPolymerization: Ring Opening Polymerization", edited by Frisch andReegen, published by Marcel Dekker in 1969, wherein stannous octanoateis an especially preferred catalyst. The catalyst is added to thereaction mixture at a concentration level of about 50 to about 10,000parts per weight of catalyst per one million parts of the total reactionmixture.

Exemplary if adducts formed by reaction of dispersant materials of thisinvention and epsilon-caprolactone are those adducts illustrated by thefollowing equation: ##STR22## wherein m and EP are as defined above. Thereactions of such lactones with multifunctional viscosity index improvermaterials containing nitrogen or ester groups is more completelydescribed in copending applications Ser. Nos. 916,108; 916,217; 916,218;916,287; 916,303; 916,113; and 916,114, all filed on Oct. 7, 1986; andcopending Ser. No. 178,099 filed on Apr. 6, 1988; the disclosure of eachof which is hereby incorporated by reference in its entirety, now U.S.Pat. Nos. 4,906,394, 4,866,141, 4,866,135, 4,866,142, 4,756,032,4,866,139, 4,963,275, with the exception of U.S. Ser. No. 916,218 whichis still pending.

Further aspects of the present invention reside in the formation ofmetal complexes of the novel multifunctional viscosity index improveradditives prepared in accordance with this invention. Suitable metalcomplexes may be formed in accordance with known techniques of employinga reactive metal ion species during or after the formation of thepresent multifunctional viscosity index improver materials. Complexforming metal reactants include the metal nitrates, thiocyanates,halides, carboxylates, phosphates, thio-phosphates, sulfates, andborates of transition metals such as iron, cobalt, nickel, copper,chromium, manganese, molybdenum, tungsten, ruthenium, palladium,platinum, cadmium, lead, silver, mercury, antimony and the like. Priorart disclosures of these complexing reactions may be also found in U.S.Pat. Nos. 3,306,908 and Re. 26,433, the disclosures of which are herebyincorporated by reference in their entirety.

The processes of these incorporated patents, as applied to thecompositions of this invention, and the post-treated compositions thusproduced constitute a further aspect of this invention.

The multifunctional viscosity index improver additives of the presentinvention can be incorporated into a lubricating oil in any convenientway. Thus, these additives can be added directly to the oil bydispersing or dissolving the same in the oil at the desired level ofconcentrations of the additive. Such blending into the additional lubeoil can occur at room temperature or elevated temperatures.Alternatively, the additives can be blended with a suitable oil-solublesolvent and base oil to form a concentrate, and then blending theconcentrate with a lubricating oil basestock to obtain the finalformulation. Such multifunctional viscosity index improver concentrateswill typically contain (on an active ingredient (A.I.) basis) from about5 to about 60 wt. %, preferably from about 10 to about 60, and morepreferably from about above 20 to about 50 wt. %, multifunctionalviscosity index improver additive, and typically from about 40 to 95 wt.%, preferably from about 40 to 80 wt. %, and more preferably from about50 to about 80 wt. % base oil, based on the concentrate weight. Thelubricating oil basestock for the multifunctional viscosity indeximprover typically is adapted to perform a selected function by theincorporation of additional additives therein to form lubricating oilcompositions (i.e., formulations).

LUBRICATING COMPOSITIONS

The additives of the present invention possess very good multifunctionalviscosity index improving, e.g., viscosity index improving-dispersant,properties in a wide variety of environments. Accordingly, the additivesare used by incorporation and dissolution into an oleaginous materialsuch as fuels and lubricating oils. When the additives of this inventionare used in normally liquid petroleum fuels such as middle distillatesboiling from about 65° to 430° C., including kerosene, diesel fuels,home heating fuel oil, jet fuels, etc., a concentration of the additivesin the fuel in the range of typically from about 0.01 to about 20, andpreferably 0.1 to about 15 weight percent, based on the total weight ofthe composition, will usually be employed.

The additives of the present invention find their primary utility inlubricating oil compositions which employ a base oil in which theadditives are dissolved or dispersed. Such base oils may be natural orsynthetic. Base oils suitable for use in preparing the lubricating oilcompositions of the present invention include those conventionallyemployed as crankcase lubricating oils for spark-ignited andcompression-ignited internal combustion engines, such as automobile andtruck engines, marine and railroad diesel engines, and the like.Advantageous results are also achieved by employing the additives of thepresent invention in base oils conventionally employed in and/or adaptedfor use as power transmitting fluids, universal tractor fluids andhydraulic fluids, heavy duty hydraulic fluids, power steering fluids andthe like. Gear lubricants, industrial oils, pump oils and otherlubricating oil compositions can also benefit from the incorporationtherein of the additives of the present invention.

These lubricating oil formulations conventionally contain severaldifferent types of additives that will supply the characteristics thatare required in the formulations. Among these types of additives areincluded viscosity index improvers, antioxidants, corrosion inhibitors,detergents, dispersants, pour point depressants, antiwear agents,friction modifiers, etc.

In the preparation of lubricating oil formulations it is common practiceto introduce the additives in the form of 10 to 80 wt. %, e.g., 20 to 80wt. % active ingredient concentrates in hydrocarbon oil, e.g. minerallubricating oil, or other suitable solvent. Usually these concentratesmay be diluted with 3 to 100, e.g., 5 to 40 parts by weight oflubricating oil, per part by weight of the additive package, in formingfinished lubricants, e.g. crankcase motor oils. The purpose ofconcentrates, of course, is to make the handling of the variousmaterials less difficult and awkward as well as to facilitate solutionor dispersion in the final blend. Thus, a multifunctional viscosityindex improver would be usually employed in the form of a 20 to 50 wt. %concentrate, for example, in a lubricating oil fraction.

The multifunctional viscosity index improvers, e.g., viscosity indeximprovers-dispersants, of the present invention will be generally usedin admixture with a lube oil basestock, comprising an oil of lubricatingviscosity, including natural and synthetic lubricating oils and mixturesthereof.

Natural oils include animal oils and vegetable oils (e.g., castor, lardoil) liquid petroleum oils and hydrorefined, solvent-treated oracid-treated mineral lubricating oils of the paraffinic, naphthenic andmixed paraffinic-naphthenic types. Oils of lubricating viscosity derivedfrom coal or shale are also useful base oils.

Alkylene oxide polymers and interpolymers and derivatives thereof wherethe terminal hydroxyl groups have been modified by esterification,etherification, etc., constitute another class of known syntheticlubricating oils. These are exemplified by polyoxyalkylene polymersprepared by polymerization of ethylene oxide or propylene oxide, thealkyl and aryl ethers of these polyoxyalkylene polymers (e.g.,methyl-poly isopropylene glycol ether having an average molecular weightof 1000, diphenyl ether of polyethylene glycol having a molecular weightof 500-1000, diethyl ether of polypropylene glycol having a molecularweight of 1000-1500); and mono- and polycarboxylic esters thereof, forexample, the acetic acid esters, mixed C₃ -C₈ fatty acid esters and C₁₃Oxo acid diester of tetraethylene glycol.

Another suitable class of synthetic lubricating oils comprises theesters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkylsuccinic acids and alkenyl succinic acids, maleic acid, azelaic acid,suberic acid, sebasic acid, fumaric acid, adipic acid, linoleic aciddimer, malonic acid, alkylmalonic acids, alkenyl malonic acids) with avariety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecylalcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycolmonoether, propylene glycol). Specific examples of these esters includedibutyl adipate, di(2-ethylhexyl)sebacate, di-n-hexyl fumarate, dioctylsebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate,didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester oflinoleic acid dimer, and the complex ester formed by reacting one moleof sebacic acid with two moles of tetraethylene glycol and two moles of2-ethylhexanoic acid.

Esters useful as synthetic oils also include those made from C₅ to C₁₂monocarboxylic acids and polyols and polyol ethers such as neopentylglycol, trimethylolpropane, pentaerythritol, dipentaerythritol andtripentaerythritol.

Silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy-, orpolyaryloxysiloxane oils and silicate oils comprise another useful classof synthetic lubricants; they include tetraethyl silicate,tetraisopropyl silicate, tetra-(2-ethylhexyl)silicate,tetra-(4-methyl-2-ethylhexyl)silicate,tetra-(p-tertbutylphenyl)silicate, hexa-(4-methyl-2-pentoxy)disiloxane,poly(methyl)siloxanes and poly(methylphenyl)siloxanes. Other syntheticlubricating oils include liquid esters of phosphorus-containing acids(e.g., tricresyl phosphate, trioctyl phosphate, diethyl ester ofdecylphosphonic acid) and polymeric tetrahydrofurans.

Unrefined, refined and rerefined oils can be used in the lubricants ofthe present invention. Unrefined oils are those obtained directly from anatural or synthetic source without further purification treatment Forexample, a shale oil obtained directly from retorting operations, apetroleum oil obtained directly from distillation or ester oil obtaineddirectly from an esterification process and used without furthertreatment would be an unrefined oil. Refined oils are similar to theunrefined oils except they have been further treated in one or morepurification steps to improve one or more properties. Many suchpurification techniques, such as distillation, solvent extraction, acidor base extraction, filtration and percolation are known to thoseskilled in the art. Rerefined oils are obtained by processes similar tothose used to obtain refined oils applied to refined oils which havebeen already used in service. Such rerefined oils are also known asreclaimed or reprocessed oils and often are additionally processed bytechniques for removal of spent additives and oil breakdown products.

Metal containing rust inhibitors and/or detergents are frequently usedwith ashless dispersants. Such detergents and rust inhibitors includethe metal salts of sulphonic acids, alkyl phenols, sulphurized alkylphenols, alkyl salicylates, naphthenates, and other oil soluble mono-and di-carboxylic acids. Usually these metal containing rust inhibitorsand detergents are used in lubricating oil in amounts of about 0.01 to10, e.g. 0.1 to 5 wt. %, based on the weight of the total lubricatingcomposition. Marine diesel lubricating oils typically employ suchmetal-containing rust inhibitors and detergents in amounts of up toabout 20 wt. %.

Highly basic alkaline earth metal sulfonates are frequently used asdetergents. They are usually produced by heating a mixture comprising anoil-soluble sulfonate or alkaryl sulfonic acid, with an excess ofalkaline earth metal compound above that required for completeneutralization of any sulfonic acid present and thereafter forming adispersed carbonate complex by reacting the excess metal with carbondioxide to provide the desired overbasing. The sulfonic acids aretypically obtained by the sulfonation of alkyl substituted aromatichydrocarbons such as those obtained from the fractionation of petroleumby distillation and/or extraction or by the alkylation of aromatichydrocarbons as for example those obtained by alkylating benzene,toluene, xylene, naphthalene, diphenyl and the halogen derivatives suchas chlorobenzene, chlorotoluene and chloronaphthalene. The alkylationmay be carried out in the presence of a catalyst with alkylating agentshaving from about 3 to more than 30 carbon atoms. For examplehaloparaffins, olefins obtained by dehydrogenation of paraffins,polyolefins produced from ethylene, propylene, etc. are all suitable.The alkaryl sulfonates usually contain from about 9 to about 70 or morecarbon atoms, preferably from about 16 to about 50 carbon atoms peralkyl substituted aromatic moiety.

The alkaline earth metal compounds which may be used in neutralizingthese alkaryl sulfonic acids to provide the sulfonates includes theoxides and hydroxides, alkoxides, carbonates, carboxylate, sulfide,hydrosulfide, nitrate, borates and ethers of magnesium, calcium, andbarium. Examples are calcium oxide, calcium hydroxide, magnesium acetateand magnesium borate. As noted, the alkaline earth metal compound isused in excess of that required to complete neutralization of thealkaryl sulfonic acids. Generally, the amount ranges from about 100 to220%, although it is preferred to use at least 125%, of thestoichiometric amount of metal required for complete neutralization.

Various other preparations of basic alkaline earth metal alkarylsulfonates are known, such as U.S. Pat. Nos. 3,150,088 and 3,150,089wherein overbasing is accomplished by hydrolysis of analkoxide-carbonate complex with the alkaryl sulfonate in a hydrocarbonsolvent-diluent oil.

A preferred alkaline earth sulfonate additive is magnesium alkylaromatic sulfonate having a total base number ranging from about 300 toabout 400 with the magnesium sulfonate content ranging from about 25 toabout 32 wt. %, based upon the total weight of the additive systemdispersed in mineral lubricating oil.

Neutral metal sulfonates are frequently used as rust inhibitors.Polyvalent metal alkyl salicylate and naphthenate materials are knownadditives for lubricating oil compositions to improve their hightemperature performance and to counteract deposition of carbonaceousmatter on pistons (U.S. Pat. No. 2,744,069). An increase in reservebasicity of the polyvalent metal alkyl salicylates and naphthenates canbe realized by utilizing alkaline earth metal, e.g. calcium, salts ofmixtures C₈ -C₂₆ salicylates and phenates (see U.S. Pat. No. 2,744,069)or polyvalent metal salts of alkyl salicyclic acids, said acids obtainedfrom the alkylation of phenols followed by phenation, carboxylation andhydrolysis (U.S. Pat. No. 3,704,315) which could then be converted intohighly basic salts by techniques generally known and used for suchconversion. The reserve basicity of these metal-containing rustinhibitors is usefully at TBN levels of between about 60 and 150.Included with the useful polyvalent metal salicylate and naphthenatematerials are the methylene and sulfur bridged materials which arereadily derived from alkyl substituted salicylic or naphthenic acids ormixtures of either or both with alkyl substituted phenols. Basicsulfurized salicylates and a method for their preparation is shown inU.S. Pat. No. 3,595,791. Such materials include alkaline earth metal,particularly magnesium, calcium, strontium and barium salts of aromaticacids having the general formula:

    HOOC--ArR.sub.1 --Xy(ArR.sub.1 OH)n                        (XIII)

where Ar is an aryl radical of 1 to 6 rings, R₁ is an alkyl group havingfrom about 8 to 50 carbon atoms, preferably 12 to 30 carbon atoms(optimally about 12), X is a sulfur (--S--) or methylene (--CH₂ --)bridge, y is a number from 0 to 4 and n is a number from 0 to 4.

Preparation of the overbased methylene bridged salicylate-phenate saltis readily carried out by conventional techniques such as by alkylationof a phenol followed by phenation, carboxylation, hydrolysis, methylenebridging a coupling agent such as an alkylene dihalide followed by saltformation concurrent with carbonation. An overbased calcium salt of amethylene bridged phenolsalicylic acid of the general Formula (XIV):##STR23## with a TBN of 60 to 150 is highly useful in this invention.

The sulfurized metal phenates can be considered the "metal salt of aphenol sulfide" which thus refers to a metal salt whether neutral orbasic, of a compound typified by the general Formula (XV): ##STR24##where x=1 or 2, n=0, 1 or 2; or a polymeric form of such a compound,where R is an alkyl radical, n and x are each integers from 1 to 4, andthe average number of carbon atoms in all of the R groups is at leastabout 9 in order to ensure adequate solubility in oil. The individual Rgroups may each contain from 5 to 40, preferably 8 to 20, carbon atoms.The metal salt is prepared by reacting an alkyl phenol sulfide with asufficient quantity of metal containing material to impart the desiredalkalinity to the sulfurized metal phenate.

Regardless of the manner in which they are prepared, the sulfurizedalkyl phenols which are useful generally contain from about 2 to about14% by weight, preferably about 4 to about 12 wt. % sulfur based on theweight of sulfurized alkyl phenol.

The sulfurized alkyl phenol may be converted by reaction with a metalcontaining material including oxides, hydroxides and complexes in anamount sufficient to neutralize said phenol and, if desired, to overbasethe product to a desired alkalinity by procedures well known in the art.Preferred is a process of neutralization utilizing a solution of metalin a glycol ether.

The neutral or normal sulfurized metal phenates are those in which theratio of metal to phenol nucleus is about 1:2. The "overbased" or"basic" sulfurized metal phenates are sulfurized metal phenates whereinthe ratio of metal to phenol is greater than that of stoichiometric,e.g. basic sulfurized metal dodecyl phenate has a metal content up toand greater than 100% in excess of the metal present in thecorresponding normal sulfurized metal phenates wherein the excess metalis produced in oil-soluble or dispersible form (as by reaction withCO₂).

Magnesium and calcium containing additives although beneficial in otherrespects can increase the tendency of the lubricating oil to oxidize.This is especially true of the highly basic sulphonates.

According to a preferred embodiment the invention therefore provides acrankcase lubricating composition also containing from 2 to 8000 partsper million of calcium or magnesium.

The magnesium and/or calcium is generally present as basic or neutraldetergents such as the sulphonates and phenates, our preferred additivesare the neutral or basic magnesium or calcium sulphonates. Preferablythe oils contain from 500 to 5000 parts per million of calcium ormagnesium. Basic magnesium and calcium sulphonates are preferred.

Viscosity modifiers impart high and low temperature operability to thelubricating oil and permit it to remain relatively viscous at elevatedtemperatures and also exhibit acceptable viscosity or fluidity at lowtemperatures. Viscosity modifiers are generally high molecular weighthydrocarbon polymers including polyesters. The viscosity modifiers mayalso be derivatized to include other properties or functions, such asthe addition of dispersancy properties. These oil soluble viscositymodifying polymers will generally have number average molecular weightsof from 10³ to 10⁶, preferably 10⁴ to 10⁶, e.g., 20,000 to 250,000, asdetermined by gel permeation chromatography or osmometry.

Examples of suitable hydrocarbon polymers include homopolymers andcopolymers of two or more monomers of C₂ to C₃₀, e.g. C₂ to C₈ olefins,including both alpha olefins and internal olefins, which may be straightor branched, aliphatic, aromatic, alkyl-aromatic, cycloaliphatic, etc.Frequently they will be of ethylene with C₃ to C₃₀ olefins, particularlypreferred being the copolymers of ethylene and propylene. Other polymerscan be used such as polyisobutylenes, homopolymers and copolymers of C₆and higher alpha olefins, atactic polypropylene, hydrogenated polymersand copolymers and terpolymers of styrene, e.g. with isoprene and/orbutadiene and hydrogenated derivatives thereof. The polymer may bedegraded in molecular weight, for example by mastication, extrusion,oxidation or thermal degradation, and it may be oxidized and containoxygen. Also included are derivatized polymers such as post-graftedinterpolymers of ethylene-propylene with an active monomer such asmaleic anhydride which may be further reacted with an alcohol, or amine,e.g. an alkylene polyamine or hydroxy amine, e.g. see U.S. Pat. Nos.4,089,794; 4,160,739; 4,137,185; or copolymers of ethylene and propylenereacted or grafted with nitrogen compounds such as shown in U.S. Pat.Nos. 4,068,056; 4,068,058; 4,146,489 and 4,149,984.

The preferred hydrocarbon polymers are ethylene copolymers containingfrom 15 to 90 wt. % ethylene, preferably 30 to 80 wt. % of ethylene and10 to 85 wt. %, preferably 20 to 70 wt. % of one or more C₃ to C₂₈,preferably C₃ to C₁₈, more preferably C₃ to C₈, alpha-olefins. While notessential, such copolymers preferably have a degree of crystallinity ofless than 25 wt. %, as determined by X-ray and differential scanningcalorimetry. Copolymers of ethylene and propylene are most preferred.Other alpha-olefins suitable in place of propylene to form thecopolymer, or to be used in combination with ethylene and propylene, toform a terpolymer, tetrapolymer, etc., include 1-butene, 1-pentene,1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, etc.; also branchedchain alpha-olefins, such as 4-methyl-1-pentene, 4-methyl-1-hexene,5-methylpentene-1, 4,4-dimethyl-1-pentene, and 6-methylheptene-1, etc.,and mixtures thereof.

Terpolymers, tetrapolymers, etc., of ethylene, said C₃₋₂₈ alpha-olefin,and a non-conjugated diolefin or mixtures of such diolefins may also beused. The amount of the non-conjugated diolefin generally ranges fromabout 0.5 to 20 mole percent, preferably from about 1 to about 7 molepercent, based on the total amount of ethylene and alpha-olefin present.

The polyester V.I. improvers are generally polymers of esters ofethylenically unsaturated C₃ to C₈ mono- and dicarboxylic acids such asmethacrylic and acrylic acids, maleic acid, maleic anhydride, fumaricacid, etc.

Examples of unsaturated esters that may be used include those ofaliphatic saturated mono alcohols of at least 1 carbon atom andpreferably of from 12 to 20 carbon atoms, such as decyl acrylate, laurylacrylate, stearyl acrylate, eicosanyl acrylate, docosanyl acrylate,decyl methacrylate, diamyl fumarate, lauryl methacrylate, cetylmethacrylate, stearyl methacrylate, and the like and mixtures thereof.

Other esters include the vinyl alcohol esters of C₂ to C₂₂ fatty or monocarboxylic acids, preferably saturated such as vinyl acetate, vinyllaurate, vinyl palmitate, vinyl stearate, vinyl oleate, and the like andmixtures thereof. Copolymers of vinyl alcohol esters with unsaturatedacid esters such as the copolymer of vinyl acetate with dialkylfumarates, can also be used.

The esters may be copolymerized with still other unsaturated monomerssuch as olefins, e.g. 0.2 to 5 moles of C₂ -C₂₀ aliphatic or aromaticolefin per mole of unsaturated ester, or per mole of unsaturated acid oranhydride followed by esterification. For example, copolymers of styrenewith maleic anhydride esterified with alcohols and amines are known,e.g., see U.S. Pat. No. 3,702,300.

Such ester polymers may be grafted with, or the ester copolymerizedwith, polymerizable unsaturated nitrogen-containing monomers to impartdispersancy to the V.I. improvers. Examples of suitable unsaturatednitrogen-containing monomers include those containing 4 to 20 carbonatoms such as amino substituted olefins asp-(betadiethylaminoethyl)styrene; basic nitrogen-containing heterocyclescarrying a polymerizable ethylenically unsaturated substituent, e.g. thevinyl pyridines and the vinyl alkyl pyridines such as 2-vinyl-5-ethylpyridine, 2-methyl-5-vinyl pyridine, 2-vinyl-pyridine, 4-vinylpyridine,3-vinyl-pyridine, 3-methyl-5-vinyl-pyridine, 4-methyl-2-vinyl-pyridine,4-ethyl-2-vinyl-pyridine and 2-butyl-1-5-vinyl-pyridine and the like.

N-vinyl lactams are also suitable, e.g. N-vinyl pyrrolidones or N-vinylpiperidones.

The vinyl pyrrolidones are preferred and are exemplified by N-vinylpyrrolidone, N-(1-methylvinyl) pyrrolidone, N-vinyl-5-methylpyrrolidone, N-vinyl-3, 3-dimethylpyrrolidone, N-vinyl-5-ethylpyrrolidone, etc.

Dihydrocarbyl dithiophosphate metal salts are frequently used asanti-wear agents and also provide antioxidant activity. The zinc saltsare most commonly used in lubricating oil in amounts of 0.1 to 10,preferably 0.2 to 2 wt. %, based upon the total weight of thelubricating oil composition. They may be prepared in accordance withknown techniques by first forming a dithiophosphoric acid, usually byreaction of an alcohol or a phenol with P₂ S₅ and then neutralizing thedithiophosphoric acid with a suitable zinc compound.

Mixtures of alcohols may be used including mixtures of primary andsecondary alcohols, secondary generally for imparting improved anti-wearproperties, with primary giving improved thermal stability properties.Mixtures of the two are particularly useful. In general, any basic orneutral zinc compound could be used but the oxides, hydroxides andcarbonates are most generally employed. Commercial additives frequentlycontain an excess of zinc due to use of an excess of the basic zinccompound in the neutralization reaction.

The zinc dihydrocarbyl dithiophosphates useful in the present inventionare oil soluble salts of dihydrocarbyl esters of dithiophosphoric acidsand may be represented by the following formula: ##STR25## wherein R andR' may be the same or different hydrocarbyl radicals containing from 1to 18, preferably 2 to 12 carbon atoms and including radicals such asalkyl, alkenyl, aryl, aralkyl, alkaryl and cycloaliphatic radicals.Particularly preferred as R and R' groups are alkyl groups of 2 to 8carbon atoms. Thus, the radicals may, for example, be ethyl, n-propyl,i-propyl, n-butyl, i-butyl, sec-butyl, amyl, n-hexyl, i-hexyl, n-octyl,decyl, dodecyl, octadecyl, 2-ethylhexyl, phenyl, butylphenyl,cyclohexyl, methylcyclopentyl, propenyl, butenyl etc. In order to obtainoil solubility, the total number of carbon atoms (i.e., R and R' inFormula XVI) in the dithiophosphoric acid will generally be about 5 orgreater.

The antioxidants useful in this invention include oil soluble coppercompounds. The copper may be blended into the oil as any suitable oilsoluble copper compound. By oil soluble we mean the compound is oilsoluble under normal blending conditions in the oil or additive package.The copper compound may be in the cuprous or cupric form. The copper maybe in the form of the copper dihydrocarbyl thio- or dithio-phosphateswherein copper may be substituted for zinc in the compounds andreactions described above although one mole of cuprous or cupric oxidemay be reacted with one or two moles of the dithiophosphoric acid,respectively. Alternatively the copper may be added as the copper saltof a synthetic or natural carboxylic acid. Examples include CIO to C₁₈fatty acids such as stearic or palmitic, but unsaturated acids such asoleic or branched carboxylic acids such as napthenic acids of molecularweight from 200 to 500 or synthetic carboxylic acids are preferredbecause of the improved handling and solubility properties of theresulting copper carboxylates. Also useful are oil soluble copperdithiocarbamates of the general formula (RR'NCSS)_(n) Cu, where n is 1or 2 and R and R' are the same or different hydrocarbyl radicalscontaining from 1 to 18 and preferably 2 to 12 carbon atoms andincluding radicals such as alkyl, alkenyl, aryl, aralkyl, alkaryl andcycloaliphatic radicals. Particularly preferred as R and R' groups arealkyl groups of 2 to 8 carbon atoms. Thus, the radicals may, forexample, be ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl,amyl, n-hexyl, i-hexyl, n-heptyl, n-octyl, decyl, dodecyl, octadecyl,2-ethylhexyl, phenyl, butylphenyl, cyclohexyl, methylcyclopentyl,propenyl, butenyl, etc. In order to obtain oil solubility, the totalnumber of carbon atoms (i.e, R and R') will generally be about 5 orgreater. Copper sulphonates, phenates, and acetylacetonates may also beused.

Exemplary of useful copper compounds are copper (Cu^(I) and/or Cu^(II))salts of alkenyl succinic acids or anhydrides. The salts themselves maybe basic, neutral or acidic. They may be formed by reacting (a) any ofthe materials discussed above in the Ashless Dispersant section, whichhave at least one free carboxylic acid (or anhydride) group with (b) areactive metal compound. Suitable acid (or anhydride) reactive metalcompounds include those such as cupric or cuprous hydroxides, oxides,acetates, borates, and carbonates or basic copper carbonate.

Examples of the metal salts of this invention are Cu salts ofpolyisobutenyl succinic anhydride (hereinafter referred to as Cu-PIBSA),and Cu salts of polyisobutenyl succinic acid. Preferably, the selectedmetal employed is its divalent form, e.g., Cu⁺². The preferredsubstrates are polyalkenyl succinic acids in which the alkenyl group hasa molecular weight greater than about 700. The alkenyl group desirablyhas a M_(n) from about 900 to 1400, and up to 2500, with a M_(n) ofabout 950 being most preferred. Especially preferred, of those listedabove in the section on Dispersants, is polyisobutylene succinic acid(PIBSA). These materials may desirably be dissolved in a solvent, suchas a mineral oil, and heated in the presence of a water solution (orslurry) of the metal bearing material. Heating may take place between70° and about 200° C. Temperatures of 110° to 140° C. are entirelyadequate. It may be necessary, depending upon the salt produced, not toallow the reaction to remain at a temperature above about 140° C. for anextended period of time, e.g., longer than 5 hours, or decomposition ofthe salt may occur.

The copper antioxidants (e.g., Cu-PIBSA, Cu-oleate, or mixtures thereof)will be generally employed in an amount of from about 50-500 ppm byweight of the metal, in the final lubricating or fuel composition.

The copper antioxidants used in this invention are inexpensive and areeffective at low concentrations and therefore do not add substantiallyto the cost of the product. The results obtained are frequently betterthan those obtained with previously used antioxidants, which areexpensive and used in higher concentrations. In the amounts employed,the copper compounds do not interfere with the performance of othercomponents of the lubricating composition, in many instances, completelysatisfactory results are obtained when the copper compound is the soleantioxidant in addition to the ZDDP. The copper compounds can beutilized to replace part or all of the need for supplementaryantioxidants. Thus, for particularly severe conditions it may bedesirable to include a supplementary, conventional antioxidant. However,the amounts of supplementary antioxidant required are small, far lessthan the amount required in the absence of the copper compound.

While any effective amount of the copper antioxidant can be incorporatedinto the lubricating oil composition, it is contemplated that sucheffective amounts be sufficient to provide said lube oil compositionwith an amount of the copper antioxidant of from about 5 to 500 (morepreferably 10 to 200, still more preferably 10 to 180, and mostpreferably 20 to 130 (e.g., 90 to 120)) part per million of added copperbased on the weight of the lubricating oil composition. Of course, thepreferred amount may depend amongst other factors on the quality of thebasestock lubricating oil.

Corrosion inhibitors, also known as anti-corrosive agents, reduce thedegradation of the metallic parts contacted by the lubricating oilcomposition. Illustrative of corrosion inhibitors are phosphosulfurizedhydrocarbons and the products obtained by reaction of aphosphosulfurized hydrocarbon with an alkaline earth metal oxide orhydroxide, preferably in the presence of an alkylated phenol or of analkylphenol thioester, and also preferably in the presence of carbondioxide. Phosphosulfurized hydrocarbons are prepared by reacting asuitable hydrocarbon such as a terpene, a heavy petroleum fraction of aC₂ to C₆ olefin polymer such as polyisobutylene, with from 5 to 30weight percent of a sulfide of phosphorus for 1/2 to 15 hours, at atemperature in the range of 65° to 315° C. Neutralization of thephosphosulfurized hydrocarbon may be effected in the manner taught inU.S. Pat. No. 1,969,324.

Oxidation inhibitors reduce the tendency of mineral oils to deterioratein service which deterioration can be evidenced by the products ofoxidation such as sludge and varnish-like deposits on the metal surfacesand by viscosity growth. Such oxidation inhibitors include alkalineearth metal salts of alkylphenolthioesters having preferably C₅ to C₁₂alkyl side chains, calcium nonylphenol sulfide, barium t-octylphenylsulfide, dioctylphenylamine, phenylalphanaphthylamine, phosphosulfurizedor sulfurized hydrocarbons, etc.

Friction modifiers serve to impart the proper friction characteristicsto lubricating oil compositions such as automatic transmission fluids.

Representative examples of suitable friction modifiers are found in U.S.Pat. No. 3,933,659 which discloses fatty acid esters and amides; U.S.Pat. No. 4,176,074 which describes molybdenum complexes ofpolyisobutenyl succinic anhydride-amino alkanols; U.S. Pat. No.4,105,571 which discloses glycerol esters of dimerized fatty acids; U.S.Pat. No. 3,779,928 which discloses alkane phosphonic acid salts; U.S.Pat. No. 3,778,375 which discloses reaction products of a phosphonatediscloses S-carboxy-alkylene hydrocarbyl succinimide, S-carboxyalkylenehydrocarbyl succinamic acid and mixtures thereof; U.S. Pat. No.3,879,306 which discloses N-(hydroxyalkyl) alkenyl-succinamic acids orsuccinimides; U.S. Pat. No. 3,932,290 which discloses reaction productsof di-(lower alkyl) phosphites and epoxides; and U.S. Pat. No. 4,028,258which discloses the alkylene oxide adduct of phosphosulfurizedN-(hydroxyalkyl) alkenyl succinimides. The disclosures of the abovereferences are herein incorporated by reference. The most preferredfriction modifiers are glycerol mono and dioleates, and succinateesters, or metal salts thereof, of hydrocarbyl substituted succinicacids or anhydrides and thiobis alkanols such as described in U.S. Pat.No. 4,344,853.

Pour point depressants lower the temperature at which the fluid willflow or can be poured. Such depressants are well known. Typical of thoseadditives which usefully optimize the low temperature fluidity of thefluid are C₈ -C₁₈ dialkylfumarate vinyl acetate copolymers,polymethacrylates, and wax naphthalene.

Foam control can be provided by an antifoamant of the polysiloxane type,e.g. silicone oil and polydimethyl siloxane.

Organic, oil-soluble compounds useful as rust inhibitors in thisinvention comprise nonionic surfactants such as polyoxyalkylene polyolsand esters thereof, and anionic surfactants such as salts of alkylsulfonic acids. Such anti-rust compounds are known and can be made byconventional means. Nonionic surfactants, useful as anti-rust additivesin the oleaginous compositions of this invention, usually owe theirsurfactant properties to a number of weak stabilizing groups such asether linkages. Nonionic anti-rust agents containing ether linkages canbe made by alkoxylating organic substrates containing active hydrogenswith an excess of the lower alkylene oxides (such as ethylene andpropylene oxides) until the desired number of alkoxy groups have beenplaced in the molecule.

The preferred rust inhibitors are polyoxyalkylene polyols andderivatives thereof. This class of materials are commercially availablefrom various sources: Pluronic Polyols from Wyandotte ChemicalsCorporation; Polyglycol 112-2, a liquid triol derived from ethyleneoxide and propylene oxide available from Dow Chemical Co.; and Tergitol,dodecylphenyl or monophenyl polyethylene glycol ethers, and Ucon,polyalkylene glycols and derivatives, both available from Union CarbideCorp. These are but a few of the commercial products suitable as rustinhibitors in the improved composition of the present invention.

In addition to the polyols per se, the esters thereof obtained byreacting the polyols with various carboxylic acids are also suitable.Acids useful in preparing these esters are lauric acid, stearic acid,succinic acid, and alkyl- or alkenyl-substituted succinic acids whereinthe alkyl-or alkenyl group contains up to about twenty carbon atoms.

The preferred polyols are prepared as block polymers. Thus, ahydroxy-substituted compound, R--(OH)n (wherein n is 1 to 6, and R isthe residue of a mono- or polyhydric alcohol, phenol, naphthol, etc.) isreacted with propylene oxide to form a hydrophobic base. This base isthen reacted with ethylene oxide to provide a hydrophylic portionresulting in a molecule having both hydrophobic and hydrophylicportions. The relative sizes of these portions can be adjusted byregulating the ratio of reactants, time of reaction, etc., as is obviousto those skilled in the art. Thus it is within the skill of the art toprepare polyols whose molecules are characterized by hydrophobic andhydrophylic moieties which are present in a ratio rendering rustinhibitors suitable for use in any lubricant composition regardless ofdifferences in the base oils and the presence of other additives.

If more oil-solubility is needed in a given lubricating composition, thehydrophobic portion can be increased and/or the hydrophylic portiondecreased If greater oil-in-water emulsion breaking ability is required,the hydrophylic and/or hydrophobic portions can be adjusted toaccomplish this.

Compounds illustrative of R--(OH)n include alkylene polyols such as thealkylene glycols, alkylene triols, alkylene tetrols, etc., such asethylene glycol, propylene glycol, glycerol, pentaerythritol, sorbitol,mannitol, and the like. Aromatic hydroxy compounds such as alkylatedmono- and polyhydric phenols and naphthols can also be used, e.g.,heptylphenol, dodecylphenol, etc.

Other suitable demulsifiers include the esters disclosed in U.S. Pat.Nos. 3,098,827 and 2,674,619.

The liquid polyols available from Wyandotte Chemical Co. under the namePluronic Polyols and other similar polyols are particularly well suitedas rust inhibitors. These Pluronic Polyols correspond to the formula:##STR26## wherein x,y, and z are integers greater than 1 such that theCH₂ CH₂ O-- groups comprise from about 10% to about 40% by weight of thetotal molecular weight of the glycol, the average molecule weight ofsaid glycol being from about 1000 to about 5000. These products areprepared by first condensing propylene oxide with propylene glycol toproduce the hydrophobic base ##STR27## This condensation product is thentreated with ethylene oxide to add hydrophylic portions to both ends ofthe molecule. For best results, the ethylene oxide units should comprisefrom about 10 to about 40% by weight of the molecule. Those productswherein the molecular weight of the polyol is from about 2500 to 4500and the ethylene oxide units comprise from about 10% to about 15% byweight of the molecule are particularly suitable. The polyols having amolecular weight of about 4000 with about 10% attributable to (CH₂ CH₂O) units are particularly good. Also useful are alkoxylated fattyamines, amides, alcohols and the like, including such alkoxylated fattyacid derivatives treated with C₉ to C₁₆ alkyl-substituted phenols (suchas the mono- and di-heptyl, octyl, nonyl, decyl, undecyl, dodecyl andtridecyl phenols), as described in U.S. Pat. No. 3,849,501, which isalso hereby incorporated by reference in its entirety.

These compositions of our invention may also contain other additivessuch as those previously described, and other metal containingadditives, for example, those containing barium and sodium.

The lubricating composition of the present invention may also includecopper lead bearing corrosion inhibitors. Typically such compounds arethe thiadiazole polysulphides containing from 5 to 50 carbon atoms,their derivatives and polymers thereof. Preferred materials are thederivatives of 1,3,4-thiadiazoles such as those described in U.S. Pat.Nos. 2,719,125; 2,719,126; and 3,087,932; especially preferred is thecompound 2,5 bis (t-octadithio)-1,3,4-thiadiazole commercially availableas Amoco 150. Other similar materials also suitable are described inU.S. Pat. Nos. 3,821,236; 3,904,537; 4,097,387; 4,107,059; 4,136,043;4,188,299; and 4,193,882.

Other suitable additives are the thio and polythio sulphenamides ofthiadiazoles such as those described in U.K. Patent Specification1,560,830. When these compounds are included in the lubricatingcomposition, we prefer that they be present in an amount from 0.01 to10, preferably 0.1 to 5.0 weight percent based on the weight of thecomposition.

Some of these numerous additives can provide a multiplicity of effects,e.g. a dispersant-oxidation inhibitor. This approach is well known andneed not be further elaborated herein.

Dispersants maintain oil insolubles, resulting from oxidation duringuse, in suspension in the fluid thus preventing sludge glocculation andprecipitation or deposition on metal parts. Suitable dispersants includehigh molecular weight alkyl succinimides, the reaction product ofoil-soluble polyisobutylene succinic anhydride with ethylene amines suchas tetraethylene pentamine and borated salts thereof.

The ashless dispersants include the polyalkenyl or borated polyalkenylsuccinimide where the alkenyl groups is derived from a C₃ -C₄ olefin,especially polyisobutenyl having a number average molecular weight ofabout 700 to 5,000. Other well known dispersants include the oil solublepolyol esters of hydrocarbon substituted succinic anhydride, e.g.,polyisobutenyl succinic anhydride, and the oil soluble oxazoline andlactone oxazoline dispersants derived from hydrocarbon substitutedsuccinic anhydride and disubstituted amino alcohols. Lubricating oilstypically contain about 0.5 to 5 wt. % of ashless dispersant.

Compositions when containing these conventional additives are typicallyblended into the base oil in amounts effective to provide their normalattendant function. Representative effective amounts of such additives(as the respective active ingredients) in the fully formulated oil areillustrated as follows:

    ______________________________________                                                         Wt. % A.I.                                                                              Wt. % A.I.                                         Compositions     (Preferred)                                                                             (Broad)                                            ______________________________________                                        Viscosity Modifier                                                                             .01-4     0.01-12                                            Detergents       0.01-3    0.01-20                                            Corrosion Inhibitor                                                                            0.01-1.5  .01-5                                              Oxidation Inhibitor                                                                            0.01-1.5  .01-5                                              Dispersant       0.1-8      .1-20                                             Pour Point Depressant                                                                          0.01-1.5  .01-5                                              Anti-Foaming Agents                                                                            0.001-0.15                                                                              .001-3                                             Anti-Wear Agents 0.001-1.5 .001-5                                             Friction Modifiers                                                                             0.01-1.5  .01-5                                              Mineral Oil Base Balance   Balance                                            ______________________________________                                    

When other additives are employed, it may be desirable, although notnecessary, to prepare additive concentrates comprising concentratedsolutions or dispersions of the novel multifunctional viscosity indeximprovers of this invention (in concentrate amounts hereinabovedescribed), together with one or more of said other additives (saidconcentrate when constituting an additive mixture being referred toherein as an additive-package) whereby several additives can be addedsimultaneously to the base oil to form the lubricating oil composition.Dissolution of the additive concentrate into the lubricating oil may befacilitated by solvents and by mixing accompanied with mild heating, butthis is not essential. The concentrate or additive-package willtypically be formulated to contain the additives in proper amounts toprovide the desired concentration in the final formulation when theadditive-package is combined with a predetermined amount of baselubricant. Thus, the dispersants of the present invention can be addedto small amounts of base oil or other compatible solvents along withother desirable additives to form additive-packages containing activeingredients in collective amounts of typically from about 2.5 to about90%, and preferably from about 15 to about 75%, and most preferably fromabout 25 to about 60% by weight additives in the appropriate proportionswith the remainder being base oil.

The final formulations may employ typically about 10 wt. % of theadditive-package with the remainder being base oil.

The amount of the multifunctional viscosity index improvers, e.g.,viscosity index improvers-dispersants, of the present invention presentin oleaginous compositions such as lubricating oil compositions is atleast a viscosity index improving effective amount, i.e., an amounteffective to improve the viscosity index of the oleaginous material. Inthe particular case of a viscosity index improver-dispersant the amountpresent is a viscosity index improving and dispersant effective amount,i.e., an amount effective to improve the viscosity index of theoleaginous material and to impart dispersance properties to saidcomposition. Generally, these amounts are usually from about 0.01 toabout 20 wt. %, preferably from about 0.05 to about 15 wt. %, morepreferably from about 0.1 to about 12 wt. %, and most preferably fromabout 0.25 to about 6 wt. %, of the total composition.

All of said weight percents expressed herein (unless otherwiseindicated) are based on active ingredient (A.I.) content of theadditive, and/or upon the total weight of any additive-package, orformulation which will be the sum of the A.I. weight of each additiveplus the weight of total oil or diluent.

This invention will be further understood by reference to the followingexamples, wherein all parts are parts by weight, unless otherwise notedand which include preferred embodiments of the invention.

EXAMPLE 1 Preparation of Ethylene Propylene Copolymer

A clean, dry autoclave is flushed with propylene and a 4 ml. solution ofmethylalumoane in toluene is added by syringe. The autoclave is thencharged with 500 ml. of liquid propylene and brought to 50° C. forreaction. The pressure in the autoclave is then increased by 150 psi byaddition of ethylene. One-half mg. of zirconocene (bis(n-butyltetrahydroindenyl)zirconium dichloride) dissolved in 3 ml. of toluene isinjected into the autoclave. Ethylene is supplied to maintain theinitial total pressure in the autoclave. Reaction time is 30 minutes.The monomers are flashed off, and the temperature is brought to 25° C.The polymer product, which has a number average molecular weight in therange of about 209,000, is recovered from the autoclave and is dried ina vacuum oven at 50° C. overnight.

EXAMPLE 2 Alkylation of Phenol

About 50 g. of ethylene-propylene copolymer is prepared substantially inaccordance with the procedure of Example 1 is dissolved in 200 ml ofchlorobenzene and added to a solution containing 10.45 g. of phenol in200 ml of chlorobenzene. While stirring at room temperature under anitrogen blanket, 0.5 g. of BF3 gas is bubbled into the chargedsolution, and the reaction mixture is stirred while the temperature isincreased to 50° C. for about 1 hour. The reaction mixture is thenneutralized with gaseous ammonia until a neutral pH is obtained. Thesolution is filtered and the filtrate is heated to 150° C. to distill ofthe solvent and excess phenol.

EXAMPLE 3 Mannich Base Condensation

Twenty-five grams of the alkylated phenol which is preparedsubstantially in accordance with the procedure of Example 2 is dissolvedin 200 g. of S150N lubricating oil. To the solution is added 0.61 g. of1,6-hexanediamine and 0.35 g. of formaldehyde at 30° C. under N₂. Themixture is heated to 115° C. and kept at that temperature for 1 hour ina four necked round bottomed flask. Then, the reaction mixture'stemperature is raised to 130° C. while the reaction vessel is swept withdry N₂ gas for 45 minutes. The stripped reaction mixture is then cooledto room temperature, diluted with 100 ml. of heptane, and filtered. Thefiltrate is then stripped at 130° C. with dry N₂ gas to remove heptane.

EXAMPLE 4

An SAE 10W40 formulation crankcase motor oil composition is prepared bydissolving sufficient Mannich Base Condensation product which isprepared substantially in accordance with the procedure of Example 3 inmineral oil to provide a composition containing 1.3 wt. % (activeingredient) of said Mannich Base condensation product. The oil alsocontains 4.3 wt. % of a detergent inhibitor package of conventionaladditives.

The principles, preferred embodiments, and modes of operation of thepresent invention have been described in the foregoing specification.The invention which is intended to be protected herein, however, is notto be construed as limited to the particular forms disclosed, sincethese are to be regarded as illustrative rather than restrictive.Variations and changes may be made by those skilled in the art withoutdeparting from the spirit of the invention.

What is claimed is:
 1. A composition useful as a multifunctionalviscosity index improver additive in oleaginous compositions whichcomprises condensation product of:(a) at least one alkyl-substitutedhydroxyaromatic compound formed by the alkylation of at least oneunsaturated ethylene alpha-olefin polymer of from greater than 25,000 toabout 500,000 number average molecular weight, said polymer containingfrom 30 to 80 weight percent ethylene and at least 30% of the polymer'schains contain terminal ethenylidene unsaturation, wherein saidhydroxyaromatic compound is represented by the formula:

    H--AR--(OH).sub.c

wherein Ar is selected from the group consisting of: ##STR28## wherein ais 1 or 2, R" is independently a halogen radical or a hydrocarbylradical containing from 1 to about 10 carbon atoms, b is independentlyan integer from 0 to 2, and c is an integer from 1 to 2; (b) at leastone aldehyde reactant selected from the group consisting of: 1.paraformaldehyde,2. C₂ to C₁₀ hydrocarbyl aldehyde, and
 3. aldehydecompounds of the formula:

    R.sup.12 CHO

wherein R¹² is H or an aliphatic hydrocarbon radical having 1 to 4carbon atoms; and (c) at least one nucleophilic reactant.
 2. Thecomposition of claim 1 wherein said polymer comprises anethylene-propylene copolymer.
 3. The composition of claim 1 wherein saidcopolymer has a number average molecular weight of from about 25,000 toabout 200,000.
 4. The composition of claim 3 wherein said number averagemolecular weight is between about 30,000 and 100,000.
 5. The compositionof claim 1 wherein said polymer has a molar ethylene content of betweenabout 20 and about 80 percent.
 6. The composition of claim 5 whereinsaid polymer has a molar ethylene content of between about 45 and about65 percent.
 7. The composition of claim wherein said hydroxy aromaticcompound comprises phenol.
 8. The composition of claim 1 wherein thenucleophilic reagent comprises an amine containing from 2 to carbonatoms and from 1 to 12 nitrogen atoms per molecule.
 9. The compositionto claim 8 wherein said amine comprises a polyalkylenepolyamine whereinsaid alkylene group contains 2 to 60 carbons and saidpolyalkylenepolyamine contains from 2 to about 9 nitrogen atoms permolecule.
 10. The composition of claim 9 wherein said amine comprisespolyethylenepolyamine.
 11. The composition of claim 8 wherein saidaldehyde reactant comprises formaldehyde.
 12. The composition of claim11 wherein said hydroxy aromatic compound comprises phenol.
 13. Thecomposition of claim 1 wherein said aldehyde reactant comprisesformaldehyde.
 14. An oil concentrate containing from about 5 to 60weight percent of the composition of claim
 1. 15. An oil concentratecontaining from about 10 to 60 weight percent of the composition ofclaim
 2. 16. A lubricating oil composition containing from about 0.01 to20 weight percent of the composition of any of claims 1 or
 2. 17. Alubricating oil composition of claim 16 containing from about 0.1 to 12weight percent of said composition.
 18. An aromatic compound useful asan oleaginous composition additive which comprises alkyl-substitutedhydroxyaromatic compound formed by the alkylation of at least onehydroxy aromatic compound with an ethylene alpha-olefin polymer fromabout 25,000 to about 500,000 number average molecular weight, saidpolymer containing from 30 to 80 weight percent ethylene and wherein atleast 30% of the polymer's chain contains terminal ethenylideneunsaturation, and wherein said hydroxyaromatic compound is representedby the formula:

    H--Ar--(OH).sub.c

wherein Ar is selected from the group consisting of: ##STR29## wherein ais 1 or 2, R" is independently a halogen radical or a hydrocarbylradical containing from 1 to about 10 carbon atoms, b is independentlyan integer from 0 to 2, and c is an integer from 1 to
 2. 19. Thearomatic compound of claim 18 wherein said polymer comprisesethylene-propylene copolymer.
 20. The aromatic compound of claim 19wherein said polymer has a number average molecular weight of betweenabout 25,000 and about 200,000.
 21. The aromatic compound of claim 20wherein said number average molecular weight is between about 30,000 and100,000.
 22. The aromatic compound of claim 18 wherein at least 60% ofthe polymer's chains contain terminal ethenylidene unsaturation.
 23. Thearomatic compound of claim 18 wherein said polymer has a molar ethylenecontent of between about and about 80 percent.
 24. The aromatic compoundof claim 23 wherein said polymer has a molar ethylene content of betweenabout 45 and about 65 percent.
 25. The aromatic compound of claim 18wherein said hydroxy aromatic compound comprises phenol.
 26. An oilconcentrate containing from about 5 to about 60 weight percent of thehydroxy aromatic compound of claim
 18. 27. An oil concentrate containingfrom about 10 to about 60 weight percent of the hydroxy aromaticcompound of claim
 18. 28. A lubricating oil composition containing amultifunctionl viscosity index improving effective amount of the hydroxyaromatic compound of claim
 18. 29. The lubricating composition of claim28 containing from about 0.01 to about 20 weight percent of said hydroxyaromatic compound.
 30. The lubricating composition of claim 29containing from about 0.1 to about 12 weight percent of said hydroxyaromatic compound.
 31. The composition of either of claims 1 and 18wherein said polymer is prepared in the presence of a catalyst systemcomprising at last one metallocene and an alumoxane compound.
 32. Themetallocene of claim 31, wherein said metallocene is a metal derivativeof cyclopentadiene.
 33. The metal derivative of cyclopentadiene of claim32, wherein said metal derivative of cyclopentadiene is selected fromthe group comprising titanium, zirconium and haphnium.
 34. Themetallocene of claim 31, wherein said metallocene is represented by theformula from the group comprising:a. (Cp)_(m) MR_(n) X_(q) wherein Cp isa cyclopentadienyl ring, M is a Group 4b transition metal, R is ahydrocarbyl group or hydrocarboxy group having from 1 to 20 carbonatoms, X is a halogen, and m is a whole number from 1 to 3, n is a wholenumber from 0 to 3, and q is a whole number from 0 to 3; b. (C₅R'_(k))_(g) R"s(C₅ R'_(k))MQ_(3-g) and c. R"_(s) (C₅ R'_(k))₂ MQ'wherein(C₅ R'_(k)) is a cyclopentadienyl or substituted cyclopentadienyl, eachR' is the same or different and is hydrogen or a hydrocarbyl radicalsuch as alkyl, alkenyl, aryl, alkylaryl, or arylalkyl radical containingfrom 1 to 20 carton atoms, a silicon containing hydrocarbyl radical, orhydrocarbyl radicals wherein two carbon atoms are joined together toform a C₄ -C₆ ring, R" is a C₁ -C₄ alkylene radical, a dialkyl germaniumor silicon, or a alkyl phosphine or amine radical bridging two (C₅R'_(k)) rings, Q is a hydrocarbyl radical such as aryl, alkyl, alkenyl,alkylaryl, or aryl alkyl radical having from 1-20 carbon atoms,hydrocarboxy radical having from 1-20 carbon atoms or halogen and can bethe same or different from each other, Q' is an alkylidene radicalhaving from 1 to about 20 carbon atoms, s is 0 or 1, g is 0, 1 or 2, sis 0 when g is 0, k is 4 when s is 1, and k is 5 when s is 0, and M isas defined above.